CN116514429A - Method for producing reducing slag-treated material, and concrete containing reducing slag-treated material - Google Patents
Method for producing reducing slag-treated material, and concrete containing reducing slag-treated material Download PDFInfo
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- CN116514429A CN116514429A CN202310058919.5A CN202310058919A CN116514429A CN 116514429 A CN116514429 A CN 116514429A CN 202310058919 A CN202310058919 A CN 202310058919A CN 116514429 A CN116514429 A CN 116514429A
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- 239000002893 slag Substances 0.000 title claims abstract description 174
- 239000000463 material Substances 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000004567 concrete Substances 0.000 title claims description 39
- 239000000203 mixture Substances 0.000 claims abstract description 54
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 claims abstract description 45
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 35
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000010583 slow cooling Methods 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 66
- 239000001569 carbon dioxide Substances 0.000 claims description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 33
- 238000010587 phase diagram Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 230000003449 preventive effect Effects 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 238000007670 refining Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000010298 pulverizing process Methods 0.000 description 11
- 239000004568 cement Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000012615 aggregate Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 102100026234 Cytokine receptor common subunit gamma Human genes 0.000 description 3
- 101710189311 Cytokine receptor common subunit gamma Proteins 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 241000009334 Singa Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- LAZOHFXCELVBBV-UHFFFAOYSA-N [Mg].[Ca].[Si] Chemical compound [Mg].[Ca].[Si] LAZOHFXCELVBBV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001719 melilite Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- 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
- C04B20/04—Heat 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
- 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
- C04B18/0481—Other specific industrial waste materials not provided for elsewhere in C04B18/00
-
- 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
-
- 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
- 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
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0231—Carbon dioxide hardening
-
- 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
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Civil Engineering (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Furnace Details (AREA)
Abstract
The present invention provides a method for preparing a reducing slag treatment material using an electric furnace reducing slag, the reducing slag treatment material being in gamma C 2 S and/or tobermorite as main components. The method for producing the reducing slag treatment material comprises a component adjustment step and a slow cooling step, and is used as wellPreparation of raw slag with gammac 2 A method for treating a material with reducing slag containing S and/or tobermorite as main components, wherein the component adjustment step adjusts the components of the reducing slag discharged from an electric furnace; the slow cooling step slowly cools the reducing slag whose components have been adjusted. Specifically, in the component adjustment step, the reducing slag is subjected to component adjustment so that the reducing slag is subjected to CaO and SiO 2 、Al 2 O 3 The weight percentage of CaO in the chemical components with the total weight percentage of MgO being 100 percent is 40 to 65 percent, and the weight percentage of SiO 2 15-45 wt% of Al 2 O 3 The weight percentage of MgO is 1-30% and the weight percentage of MgO is 5-15%. In the slow cooling step, the reducing slag whose composition has been adjusted is slowly cooled in a reducing atmosphere.
Description
Technical Field
The present invention relates to a method for producing a reducing slag-treated material, and concrete containing a reducing slag-treated material, and more particularly to a method for producing a reducing slag-treated material using γC 2 S(γ-2CaO·SiO 2 ) And/or tobermorite (3CaO.MgO.2SiO) 2 ) A method for producing a reducing slag-treated material which is a main component, a reducing slag-treated material, and concrete containing a reducing slag-treated material.
Background
Conventionally, cement has been used in a large amount as a raw material of concrete, and fossil fuel or the like has been used in the production process of cement, and thus, it is a material with a large carbon dioxide emission amount. Therefore, as a ring of measures against global warming, it is required to reduce the amount of carbon dioxide discharged when producing concrete.
In this process, the following inventions have been proposed: use of γc which readily reacts with carbon dioxide 2 S or tobermorite is used as an additive, kneaded with a small amount of water, cement and aggregate (fine and coarse), and hardened by absorbing carbon dioxide at a high concentration, whereby a large amount of carbon dioxide is fixed to the cement-based material (concrete) inside (see patent document 1 and non-patent document 1).
Patent document 1: japanese patent application laid-open No. 2011-168436
Non-patent document 1: cheng Gangshi "study on cement-based materials having self-defense function for neutralization", civil engineering works, concrete technical series No.74, and small committee report on physical property change and performance of concrete using a mixed material, seminar lecture summary set, non-patent document 2 in 2007: "development and test construction according to EIEN", concrete engineering, vol.45, no.7, p.31-37, 2007 ", all of high durability technology for concrete cured by carbonation", et al, bian Xian
Disclosure of Invention
Thus, γC 2 S and tobermorite can be key materials for building carbon neutralization or carbon negative society.
On the other hand, preparation of γC 2 In the case of S, for example, limestone or silica is mixed, and the mixture is calcined at 1200 to 1400 ℃ after adjusting the components, which is a relatively expensive material, and thus there is a problem that mass production is difficult. The same applies to tobermorite.
In addition, gamma C is prepared 2 In the case of S or tobermorite, decarbonization and oxidation treatment of limestone and the use of a large amount of fossil fuel are indispensable, and therefore, there is a problem that the amount of carbon dioxide discharged is higher than the amount of carbon dioxide absorbed (fixed amount), and carbon is thus directly oxidized.
Therefore, there is a need for a technique that can effectively obtain gamma C 2 S or tobermorite as a main component, while not emitting carbon dioxide when preparing the composition.
However, there is an electric furnace reducing slag, which has a composition similar to γC 2 S or a material of similar chemical composition to tobermorite. In iron industry, electric furnace reducing slag and electric furnace oxidizing slag are produced in a refining process for regenerating scrap iron as a main raw material. At present, electric furnace reducing slag is mixed with electric furnace oxidizing slag and used as a civil engineering material with low added value.
Therefore, in the iron-making industry and the steel-making/rolling industry, there is a need for effective use of the reducing slag discharged from the electric furnace, that is, for application to materials with high added value.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a reducing slag treated material, which can efficiently produce gamma C using an electric furnace reducing slag 2 S or tobermorite as a main component.
Another object of the present invention is to provide the reducing slag treatment material and a concrete containing the reducing slag treatment material, wherein the concrete contains the reducing slag treatment material and can favorably fix carbon dioxide.
The inventors of the present invention have conducted extensive and intensive effortsResearch has found that γC in conventional electric furnace reducing slag discharged from an electric furnace 2 S and/or tobermorite are contained in a small amount, but gamma C can be efficiently produced by adjusting the composition of the reducing slag under a certain condition and slowly cooling 2 S and/or tobermorite as main components.
In addition, if the preparation method is the preparation method, a cement-based material (concrete) that can fix carbon dioxide well can be realized without using fossil fuel as in the past, and a carbon-neutral (carbon-negative) society can be realized, which has led to the generation of the present invention.
Accordingly, the above-described problems are solved by the following means. According to the present invention, there is provided a method for preparing gamma C using reducing slag discharged from an electric furnace 2 S(γ-2CaO·SiO 2 ) And/or tobermorite (3CaO.MgO.2SiO) 2 ) The method for treating the material with the reducing slag as the main component comprises a component adjustment step of adjusting the component of the reducing slag so as to adjust the components of CaO and SiO 2 、Al 2 O 3 The weight percentage of CaO in the chemical components with the total weight percentage of MgO being 100 percent is 40 to 65 percent, and the weight percentage of SiO 2 15-45 wt% of Al 2 O 3 1-30% by weight of MgO, 5-15% by weight of MgO, and the total weight of all components is 100%; the slow cooling step slowly cools the reducing slag whose composition has been adjusted in a reducing atmosphere.
In this case, it is preferable that the reducing slag is subjected to component adjustment in the component adjustment step so as to be composed of CaO and SiO 2 Is mainly composed of CaO and SiO 2 、Al 2 O 3 The chemical composition of MgO is 100% by weight, caO is 45-62% by weight, siO 2 Is 20-40% by weight of Al 2 O 3 2-23 wt% and 5-15 wt% of MgO.
In the composition adjustment step, the reducing slag is preferably adjusted so as to be in CaO-SiO 2 -Al 2 O 3 (weight percent of mgo=10%) C in the ternary phase diagram 2 Composition of primary crystal region of S.
In the slow cooling step, the reducing slag whose composition has been adjusted is preferably slowly cooled at a temperature gradient of 20 ℃/min or less in a range of 400 to 800 ℃.
In the slow cooling step, it is preferable that γc contained in the reducing slag after the composition adjustment be obtained 2 S, not added for preventing secondary alpha C 2 S and/or beta C 2 S-direction gamma C 2 S converted slag dust preventive.
The above problems are solved as follows. According to the invention, is a gamma C 2 Reducing slag treatment material with S and/or magnesia-silica-lime as main components and prepared from CaO and SiO 2 、Al 2 O 3 The weight percentage of CaO in the chemical components with the total weight percentage of MgO being 100 percent is 40 to 65 percent, and the weight percentage of SiO 2 15-45 wt% of Al 2 O 3 1-30% by weight of MgO, 5-15% by weight of MgO, and 100% by weight of each component in CaO-SiO 2 -Al 2 O 3 (weight percent of mgo=10%) C in the ternary phase diagram 2 Composition of primary crystal region of S.
The above problems are solved as follows. According to the present invention, there is a concrete containing a reducing slag treatment material prepared by the above-described preparation method and fixing carbon dioxide.
According to the present invention, it is possible to provide a production method of a reducing slag treatment material, which can efficiently produce gamma C using an electric furnace reducing slag 2 S and/or tobermorite as main components.
In addition, the reducing slag treatment material and concrete containing the reducing slag treatment material, which contains the reducing slag treatment material and can favorably fix carbon dioxide, can be provided.
Drawings
FIG. 1 is CaO-SiO 2 -Al 2 O 3 Ternary phase diagram (weight percent MgO = 10%).
FIG. 2 shows a confirmation γC 2 S and abundance of tobermorite, and confirming the carbon dioxide activity, test results of test example 1.
Detailed Description
Hereinafter, an embodiment of the present invention will be described with reference to fig. 1 to 2.
The present embodiment is an invention related to "a method for producing a reducing slag treatment material", and is mainly characterized in that: comprises a 'component adjustment step' for adjusting the components of the reducing slag discharged from the electric furnace, and a 'slow cooling step' for slowly cooling the reducing slag after component adjustment, and gamma C is produced using the reducing slag 2 S and/or tobermorite as main components.
The present invention relates to "reducing slag treatment material" and "concrete containing reducing slag treatment material".
< reducing slag treatment Material >
In the iron and steel smelting process, there are a blast furnace, a converter, and an electric furnace smelting method, in which "blast furnace slag" and "converter slag" are discharged from the former and "electric furnace slag" is discharged from the latter, respectively.
In an electric furnace, iron scrap (scrap iron) as a main raw material is melted by heating from the outside, and steel is made by oxidation refining and reduction refining. Slag generated in the oxidation refining process is called "oxidizing slag", slag generated in the reduction refining process is called "reducing slag", and the oxidizing slag and the reducing slag are collectively called "electric slag".
"oxidizing slag" is slag generated when molten steel is stirred during oxidation refining. The oxide slag contains about 30% iron oxide dissolved in metallic iron and slag, and is a relatively high density hard slag.
The "reducing slag" is slag generated in the reduction refining process of removing oxygen in molten steel by discharging oxidizing slag, charging slaked lime, and the like after oxidation refining.
The reducing slag is like blast furnace slag and is CaO-SiO 2 -Al 2 O 3 -a composition comprising MgO as main component. C contained in the reducing slag 2 When S is converted from alpha phase or beta phase to gamma phase of low temperature transformation, the low density causes desertification (pulverization) and the subsequent processing becomes difficult (for example, alkalinity CaO/SiO) 2 More than about 1.5 times the weight of the slag having a composition passing through 2CaO/SiO during its cooling 2 The property of phase transition from the alpha or beta phase to the gamma phase). Therefore, a fluorine-based or boron-based slag pulverization inhibitor is usually added to suppress the conversion from the α -phase or β -phase to the γ -phase, and the slag is kept cooled.
Reaction 1
For example, as shown in the above reaction scheme, the transformation to gamma phase occurs at a transformation temperature of 675 ℃, the volume becomes about 1.12 times, the whole block expansion is pulverized, and the reaction is C with poor handleability 2 S material. In addition, conversely, γc is easily obtained in the reducing slag discharged from the electric furnace 2 S.
In general, reducing slag discharged from an electric furnace (which is kept in a lump and cooled) is mixed with oxidizing slag, and after hydration-curing of unreacted components such as unreacted free lime (f-CaO), the mixture is used as a civil engineering material such as a roadbed material.
“γC 2 S' is also called gamma dicalcium silicate, which is a type of calcium silicate prepared by gamma-2 CaO.SiO 2 A material representing a chemical composition. In addition, caO-SiO is shown in FIG. 1 2 -Al 2 O 3 The ternary phase diagram (weight percent of mgo=10%) is "C 2 Composition of the primary crystalline region of S ".
γC 2 S is a carbon dioxide active material which is not normally hydrated but is a highly valuable material for use as a concrete admixture. Specifically, by combining γC 2 S is kneaded with water, a small amount of cement and aggregate (fine and coarse) to form mortar and concrete, and then brought into contact with carbon dioxide having a high concentration (for example, 5 to 20%) to thereby enable a short timeHardened mortar/concrete having normal strength is obtained in (for example, five days or so). In this case, a large amount of carbon dioxide can be fixed to the concrete.
γC 2 S is generally obtained by pulverizing limestone and silica, and then pulverizing the material obtained after calcination at 1200-1400 ℃ using a rotary kiln. At this time, unreacted CaO remains if the temperature is low, and βC which undergoes a high-temperature transformation if the temperature is high 2 S, S. In particular, the more the treatment in an oxidizing atmosphere, the more the βc 2 The more likely S remains.
In addition, limestone is used as a main raw material, and calcination requires a large amount of fossil fuel. Therefore, even if the conventional preparation method tries to prepare γc 2 S is used as a material for fixing carbon dioxide, but in the production of gammaC 2 S already results in a positive carbon.
"Merwinite" is a compound of 3 CaO. MgO.2SiO 2 A material representing a chemical composition. In addition, the composition of the primary crystal region of "tobermorite" is shown in the ternary phase diagram of fig. 1.
Tobermorite and gamma C 2 S is the same as S, is a carbon dioxide active material, and is a material with high utilization value as a concrete additive.
The "reducing slag treatment material" of the present embodiment is a material prepared by using γC 2 Composition containing S and/or tobermorite as main components, wherein the main chemical components comprise CaO and SiO 2 、Al 2 O 3 MgO. In addition, chemical components derived from the reducing slag may be further included, and chemical components derived from additives or modifiers (e.g., refining aids) may be further included.
(chemical composition)
The reducing slag treatment material is prepared from CaO and SiO 2 、Al 2 O 3 Of the chemical components of 100% by weight of MgO, 30 to 70% by weight of CaO, preferably 35 to 70% by weight, more preferably 40 to 65% by weight, still more preferably 45 to 62% by weight, still more preferably 47 to 62% by weight, still more preferably by weightThe weight percentage is 55-62%.
In addition, among the above chemical components, siO 2 Is 10-50% by weight, preferably 15-45% by weight, more preferably 18-45% by weight, still more preferably 20-40% by weight, still more preferably 28-31% by weight.
In addition, among the above chemical components, al 2 O 3 Is 1 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 23% by weight, still more preferably 2 to 15% by weight, still more preferably 2 to 13% by weight, still more preferably 5 to 10% by weight.
In addition, among the above chemical components, mgO is 1 to 20% by weight, preferably 5 to 15% by weight, and more preferably 5 to 10% by weight.
That is, the reducing slag treatment material more preferably has CaO content of 55 to 62% by weight and SiO content in the above chemical components 2 28-31 wt% of Al 2 O 3 The weight percentage of MgO is 5-10%, and the total weight percentage of each component is 100%.
If the chemical component is the above chemical component, the gamma C can be obtained 2 S and/or tobermorite is a reducing slag treatment material having a high content of the main component (main product).
At this time, by adding SiO 2 And Al 2 O 3 These two components can give γC 2 S and the reducing slag with higher content of the magnesia-tobermorite.
In addition, by making SiO 2 Composition ratio Al 2 O 3 More components, can obtain gammaC 2 S and the reducing slag with higher content of the magnesia-tobermorite.
In addition, by making MgO component ratio Al 2 O 3 The components are more, and the reducing slag treatment material with higher content of the tobermorite can be obtained.
(crystalline state)
The reducing slag treatment material is preferably CaO-SiO as shown in FIG. 1 2 -Al 2 O 3 The ternary phase diagram (weight percent of mgo=10%) is "C 2 S "or" tobermorite ". Further preferred is "C 2 Composition of the primary crystalline region of S ".
Thus, gamma C can be obtained 2 S and/or tobermorite is a reducing slag treatment material having a high content of the main component (main product).
Here, the weight percentage of mgo=10%, but is not particularly limited, and as described above, the weight percentage of MgO is 1 to 20%, preferably 5 to 15%.
In addition, the reducing slag treatment material may not be "C 2 Composition of the crystalline region of S "or" tobermorite ". For example, in the ternary phase diagram shown in FIG. 1, it may be "C 2 S "or" tobermorite "around the crystallization zone. Alternatively, the reducing slag treatment material having the above chemical composition may be used regardless of the crystalline state. Even in this case, gamma C can be obtained 2 S and/or tobermorite as main components.
< concrete containing reducing slag Material >
The "concrete containing the reducing slag treatment material" of the present embodiment is a concrete containing the reducing slag treatment material and fixing carbon dioxide.
Specifically, after kneading water, cement, aggregate (fine and coarse) and a reducing slag-treated material as an admixture to form mortar and concrete, the concrete containing the reducing slag-treated material can be obtained by curing with a high concentration (for example, 5 to 20%) of carbon dioxide.
A large amount of carbon dioxide is fixed to the concrete containing the reducing slag treatment material, and the greater the fixed amount of carbon dioxide, the higher the compressive strength of the concrete.
< preparation method of reducing slag Material >
Next, the "component adjustment step" and the "slow cooling step" performed by the production method of the present embodiment will be described in detail. Further, other steps may be appropriately performed by known techniques.
In the "component adjustment step", caO and SiO as reducing slag generated in the electric furnace are treated 2 、Al 2 O 3 The chemical composition of MgO is adjusted so that it is the chemical composition described above.
To describe in detail, in order to suppress Al 2 O 3 Increasing MgO component to make CaO and SiO 2 As a main component, a refining aid is added to the electric furnace to adjust the composition of the reducing slag. For example, mn alloy, feO, steel-making slag, or the like can be used as a refining aid.
In addition to the above-described refining aids, the chemical composition of the reducing slag may be adjusted by other adjustment methods.
It is preferable to maintain a reducing atmosphere in the electric furnace.
In addition, in the "component adjustment step", the component adjustment is performed so as to be in CaO-SiO 2 -Al 2 O 3 The ternary phase diagram (weight percent of mgo=10%) is "C 2 Composition of the primary crystalline region "of S.
In detail, it is known that the reducing slag generated in the electric furnace has a phase diagram of "C" as shown in FIG. 1 2 The approximate chemical composition of the primary crystalline region of S ". In order to bring the chemical composition of the reducing slag close to C 2 S(CaO：65％、SiO 2 : 35%) and the reducing slag is subjected to composition adjustment by adding raw materials such as slaked lime, dolomite and/or silica to the electric furnace. In this way, the composition of the reducing slag can be adjusted to C 2 And S is in the primary crystal region.
In addition, mgO is necessary for protecting the refractory of the electric furnace. By supplying MgO, except γC 2 S, the tobermorite can be obtained at the same time.
In the "slow cooling step", the reducing slag whose composition has been adjusted is slowly cooled in a reducing atmosphere in an electric furnace, taken out from the electric furnace, and then slowly cooled at a temperature gradient of 20 ℃/min or less in the range of 400 to 800 ℃.
In detail, in order to maintain the reducing atmosphere in the furnace, the upper surface is covered with rice hulls or the like to maintain the heat-insulating state. In addition, cold air blowing or water spraying is avoided as much as possible. In addition, the reducing atmosphere may be maintained by other means than the above.
By maintaining the reducing atmosphere in this manner, metal ions such as iron are reduced to metal, and solid solution in the reducing slag can be suppressed. Can effectively obtain gammac 2 S and/or the reducing slag with high content of the magnesium-silicon-calcium stone.
Furthermore, γC 2 S and alpha C 2 S and beta C 2 S is smaller than the solid solubility limit (solid solubility limit) of the impurity. Therefore, by making C contained in the reducing slag 2 S is converted into a gamma phase state of low-temperature phase transformation, so that the S can be further inhibited from being dissolved in the reducing slag, and the reducing slag treatment material with less impurities is obtained.
In the "slow cooling step", a heating operation or a heat-insulating operation is performed around the transformation temperature (about 675 ℃) from the beta phase to the gamma phase, and the gamma C can be obtained by slowing down the temperature gradient 2 Reducing slag treatment materials with high S content. If the cooling rate is too high, it will result in beta C 2 S content is increased, gammaC 2 The S content is reduced.
Thus, in particular, after removal from the electric furnace, it is slowly cooled with a gentle temperature gradient in the range 650-700 ℃, preferably in the range 600-750 ℃, more preferably in the range 600-800 ℃, even more preferably in the range 500-800 ℃, still more preferably in the range 400-800 ℃.
In the above temperature range, the cooling is performed slowly with a temperature gradient of 30 ℃/min or less, preferably 20 ℃/min or less, more preferably 15 ℃/min or less, and even more preferably 10 ℃/min or less.
In the "slow cooling step", γc included in the reducing slag after the component adjustment is not added 2 S-direction alpha C 2 S and/or beta C 2 S converted slag dust preventive.
In detail, in the past, in order to improve the handleability of the cooled reducing slag and to suppress C 2 Slag pulverization prevention agents such as sodium borate are added to the slag pulverization accompanying the conversion of S from β phase to γ phase. However, in the present embodiment, the purpose is to effectively obtain γc 2 Reducing slag treatment materials with high S content. Therefore, it is preferable that the reducing slag is cooled slowly without adding the slag powder preventing agent.
The slag powder preventive agent is not limited to sodium borate, and may be fluorine-based or boron-based, or may be other powder preventive agent, or may not be added. Alternatively, no additives for preventing gamma C 2 S conversion additive and regulator.
In the "slow cooling step", the reducing slag whose composition has been adjusted is slowly cooled in the reducing atmosphere in the electric furnace, and is not necessarily slowly cooled in the reducing atmosphere after being taken out from the electric furnace. That is, the cooling may be slow in an oxidizing atmosphere outside the electric furnace.
In addition, the cooling can be performed conventionally in the electric furnace and slowly outside the electric furnace.
As described above, γc can be produced from the reducing slag produced in the electric furnace by the "component adjustment step", the "slow cooling step" and other treatment steps 2 S and/or tobermorite as main components.
In particular, according to the present production method, the reducing slag discharged from the electric furnace can be directly treated to obtain the reducing slag treated material.
Examples
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the present embodiment.
< examples: reducing slag treatment Material)
Based on the above-described method for producing a reducing slag-treated material, as shown in fig. 2, under different conditions of (1) chemical composition, (2) crystalline state, (3) cooling method, (4) addition of a pulverization preventing material, and (5) redox atmosphere, an attempt was made to produce a reducing slag-treated material using the reducing slag discharged from the electric furnace at the same time.
Specifically, regarding (1) chemical composition, the reducing slag is subjected to composition adjustment so as to form CaO and SiO 2 、Al 2 O 3 MgO has different chemical compositions. In addition, in the reducing slag treatment material, caO-SiO 2 -Al 2 O 3 The weight percentage of the chemical components of MgO is more than 90% in total, so that the ratio is calculated in this example with the total of their content being 100% by weight. FIG. 1 is a schematic diagram of CaO-SiO 2 -Al 2 O 3 Ternary phase diagram with 10% by weight of MgO added.
Regarding the crystalline state (2), if C is shown as a thick frame in the ternary phase diagram shown in FIG. 1 2 The composition of the primary crystal region of S is marked "O", and the composition of the primary crystal region is marked "X". Furthermore, caO-SiO is concerned 2 -Al 2 O 3 C in MgO series 2 Chemical composition of primary crystal region of S, weight percentage of CaO: 45-65% of SiO 2 Is prepared from the following components in percentage by weight: 20-40% of Al 2 O 3 Is prepared from the following components in percentage by weight: 5-23% of MgO in percentage by weight: 5-15%. Further, taking into account composition changes and the like in the electric furnace, al 2 O 3 If the number is 1-30%, mark is marked with "O".
In the cooling method (3), the upper surface of the furnace is covered with rice hulls, and the reducing slag is cooled while maintaining the heat-insulating state. In addition, no cold air or water spray is blown. At this time, the reducing slag was slowly cooled at a temperature gradient of 20 ℃ per minute or less in the range of 400 to 800 ℃ and marked with "o", and the normal cooling was marked with "x".
Regarding (4) whether or not the pulverization preventing material is added, a material for suppressing γC is added 2 The slag powder preventive agent (sodium borate) which was pulverized with the generation of S was marked "o" and the mark was not added "x".
Regarding (5) the redox atmosphere, the mark "o" in which the reducing atmosphere slowly cools the reducing slag is maintained, and the mark "x" in which the reducing atmosphere slowly cools the reducing slag is not maintained.
In this example, the reducing slag treatment materials of examples 1 to 18 were prepared under the different conditions of (1) to (5) described above.
< test example 1: evaluation test ]
Preparation of the reducing slag-treated materials of example 1-example 18 shown in FIG. 2 was carried out while evaluating γC 2 S and tests of abundance of tobermorite and activity of carbon dioxide.
First, in order to evaluate γc contained in the reducing slag treatment material of each example 2 And (3) carrying out powder X-ray diffraction analysis on the reducing slag treatment material by using Cu-K alpha rays according to the abundance of S and tobermorite (C3 MS 2). That is, γC is determined by detecting the main peak 2 S and presence or absence of tobermorite, and γC was determined 2 Abundance of S and tobermorite.
At this time, it was found that γC was present 2 S and/or tobermorite, in terms of total abundance, the content is the most marked "+++", the content is high marked "+++", the corresponding containing label "++". In addition, in the case of the optical fiber, although the above-mentioned evaluation is not achieved the price "+++" - "++++", but there is gamma C 2 S and/or tobermorite, on the other hand, is marked "+", if not present.
Next, in order to evaluate the carbon dioxide activity of the reducing slag treatment material of each example, concrete containing the reducing slag treatment material was prepared using the reducing slag treatment material as an additive, and the compressive strength of the concrete was calculated. Further, the more the fixed amount of carbon dioxide fixed in the concrete, the higher the compressive strength of the concrete.
Specifically, the reducing slag-treated material was pulverized by using a known test pulverizer so that the Boehringer's specific surface area was 4000cm 2 And adjusting the powder degree to make the slag particles after crushing to be below 50 mu m. Then, water (tap water), ordinary portland cement (manufactured by Taiheiyo Cement Group), fine aggregate (Liu Sha from the well river of the county of singa, surface dry density: 2.59g/cm 3 F.m.:2.71 In a mass ratio of 0.5:0.5:2.0:0.5 (water: and (3) cement: aggregate: reducing slag treated material), weighing, and kneading. Then, a mortar of 4 cm. Times.4 cm. Times.16 cm was prepared, and after demolding for 1 day, the mortar was cooled to a carbon dioxide concentration of 20% and a phase of 20%The mortar is subjected to wet air curing for 5 days in a curing tank with the humidity of 100% and the temperature of 40 ℃. After curing, the compressive strength is measured (for measurement of compressive strength, refer to non-patent document 2).
For the measurement results of the concrete using each example, the compressive strength was marked "good" at 20MPa or more, the compressive strength was marked "good" at 10 to 20MPa, and the compressive strength was marked "X" at 10MPa or less, based on the practical strength of the concrete product.
(results and study of test example 1)
Summarizing γc in each example 2 The results of evaluation of the abundance of S and/or tobermorite and the results of evaluation of carbon dioxide activity are shown in fig. 2.
From the test results of test example 1, it was revealed that γC was present in the main products of the reducing slag treatment materials of examples 1, 4 to 16 2 S and/or tobermorite.
It is also evident that examples 1, 4-12 contain a corresponding amount of γC or more 2 S and/or tobermorite.
On the other hand, in example 2, the chemical composition was the same as in example 1, but since the pulverization preventive was added, βc which did not exhibit carbon dioxide activity was obtained 2 S content is high, almost no or no gamma C 2 S, S. That is, it was found that the addition of the pulverization preventive suppressed γC 2 S and/or the generation of the tobermorite.
For example 3, although the chemical composition was the same as that of example 1, no gamma C reaction occurred due to normal cooling (rapid cooling) 2 S conversion, containing beta C 2 S, hardly containing or not containing gamma C 2 S, S. That is, it was found that the cooling method inhibited γC 2 S and/or the generation of the tobermorite.
For examples 13-16, the crystalline state is C 2 S is outside the composition of the primary crystal region, and thus, although γC is detected 2 S peaks, but CaO, mgO, and melilite are the main products. That is, it was found that the crystallization state inhibited γC 2 S and/or the generation of the tobermorite.
In examples 17 and 18, since the reducing atmosphere was not maintained but the oxidizing atmosphere was maintained, the following was adoptedγC 2 The amount of S produced is suppressed to a low level. Namely, it was found that the redox atmosphere inhibited γC 2 S and/or the generation of the tobermorite.
Further, the test results of test example 1 show that the use of γC 2 The concrete of examples 1 and 4 to 12, in which S and/or tobermorite were the main components, had a compressive strength of 20MPa or more. Namely, the carbon dioxide activity (carbon dioxide fixation amount) is higher.
For the concrete using examples 13 to 16, the compressive strength was 10MPa or more. I.e. the carbon dioxide activity is higher.
On the other hand, for examples 2, 3, 17, 18, no compressive strength based on the above criteria could be obtained. I.e. the carbon dioxide activity is low.
The above shows that, in the above-mentioned method for producing a reducing slag-treated material, by optimizing the conditions of (1) chemical composition, (2) crystal state, (3) cooling method, (4) addition of a pulverization preventing material or not, and (5) redox atmosphere, γc can be efficiently produced 2 Reducing slag treatment material containing S and/or tobermorite as main components, and concrete containing the reducing slag treatment material.
Claims (7)
1. A method for preparing a reducing slag treated material, which is a method for preparing gamma C by using reducing slag discharged from an electric furnace 2 S(γ-2CaO·SiO 2 ) And/or tobermorite (3CaO.MgO.2SiO) 2 ) A method for treating a material with a reducing slag as a main component, characterized by:
comprises a component adjusting procedure and a slow cooling procedure;
the component adjustment step adjusts the components of the reducing slag so as to adjust the components of CaO and SiO 2 、Al 2 O 3 The weight percentage of CaO in the chemical components with the total weight percentage of MgO being 100 percent is 40 to 65 percent, and the weight percentage of SiO 2 15-45 wt% of Al 2 O 3 1-30% by weight of MgO, 5-15% by weight of MgO, and the total weight of all components is 100%;
the slow cooling step slowly cools the reducing slag whose composition has been adjusted in a reducing atmosphere.
2. The method for producing a reducing slag treatment material according to claim 1, characterized in that:
in the component adjustment step, the reducing slag is subjected to component adjustment so as to obtain CaO and SiO 2 Is mainly composed of CaO and SiO 2 、Al 2 O 3 The chemical composition of MgO is 100% by weight, caO is 45-62% by weight, siO 2 Is 20-40% by weight of Al 2 O 3 2-23 wt% and 5-15 wt% of MgO.
3. The method for producing a reducing slag treatment material according to claim 1 or 2, characterized in that:
in the component adjustment step, the reducing slag is subjected to component adjustment so as to be in CaO-SiO 2 -Al 2 O 3 (weight percent of mgo=10%) C in the ternary phase diagram 2 Composition of primary crystal region of S.
4. The method for producing a reducing slag treatment material according to claim 1, characterized in that:
in the slow cooling step, the reducing slag whose composition has been adjusted is slowly cooled at a temperature gradient of 20 ℃/min or less in a range of 400-800 ℃.
5. The method for producing a reducing slag treatment material according to claim 1, characterized in that:
in the slow cooling step, no γc for promoting the inclusion of the reducing slag after component adjustment is added 2 S-direction alpha C 2 S and/or beta C 2 S converted slag dust preventive.
6. A reducing slag treating material is prepared from gamma C 2 S and/or tobermorite (3CaO.MgO.2SiO) 2 ) At the reducing slag as the main componentThe material is characterized in that:
in CaO, siO 2 、Al 2 O 3 The weight percentage of CaO in the chemical components with the total weight percentage of MgO being 100 percent is 40 to 65 percent, and the weight percentage of SiO 2 15-45 wt% of Al 2 O 3 1-30% by weight of MgO, 5-15% by weight of MgO, and the total weight of all components is 100%;
it is formed from CaO-SiO 2 -Al 2 O 3 (weight percent of mgo=10%) C in the ternary phase diagram 2 Composition of primary crystal region of S.
7. A concrete containing a reducing slag treatment material, characterized in that:
a reducing slag treatment material according to claim 6, wherein carbon dioxide is fixed.
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| JP2004292201A (en) | 2003-03-26 | 2004-10-21 | Denki Kagaku Kogyo Kk | Admixture for concrete and concrete composition |
| EP2468388B1 (en) | 2006-03-10 | 2013-09-25 | C-Quest Technologies International LLC | Carbon dioxide sequestration processes |
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