CN113213788A - Composite cement with few silicate clinker components and preparation method thereof - Google Patents
Composite cement with few silicate clinker components and preparation method thereof Download PDFInfo
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- CN113213788A CN113213788A CN202110318368.2A CN202110318368A CN113213788A CN 113213788 A CN113213788 A CN 113213788A CN 202110318368 A CN202110318368 A CN 202110318368A CN 113213788 A CN113213788 A CN 113213788A
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- 239000004568 cement Substances 0.000 title claims abstract description 99
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 42
- 235000019738 Limestone Nutrition 0.000 claims abstract description 32
- 239000006028 limestone Substances 0.000 claims abstract description 32
- 239000002893 slag Substances 0.000 claims abstract description 32
- 239000010881 fly ash Substances 0.000 claims abstract description 31
- 239000011398 Portland cement Substances 0.000 claims abstract description 29
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 29
- 239000010440 gypsum Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 claims abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 41
- 239000011707 mineral Substances 0.000 claims description 41
- 235000010755 mineral Nutrition 0.000 claims description 35
- -1 alkali metal salt Chemical class 0.000 claims description 33
- 238000000227 grinding Methods 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052593 corundum Inorganic materials 0.000 claims description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000292 calcium oxide Substances 0.000 claims description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229940044172 calcium formate Drugs 0.000 claims description 8
- 239000004281 calcium formate Substances 0.000 claims description 8
- 235000019255 calcium formate Nutrition 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011573 trace mineral Substances 0.000 claims description 5
- 235000013619 trace mineral Nutrition 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000004567 concrete Substances 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000003469 silicate cement Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011404 masonry cement Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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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
- 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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing activators
- C04B7/19—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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the technical field of cementing materials, and discloses a composite cement with less silicate clinker components and a preparation method thereof, wherein the composite cement with less silicate clinker components comprises the following preparation raw materials: portland cement clinker, gypsum, slag powder, fly ash, limestone powder and aluminosilicate mineral powder; the obtained composite cement has less silicate clinker consumption, clinker components can be as low as about 30%, the total amount of mixed material components of slag, fly ash, pozzolana, industrial solid waste, limestone and the like can be as high as about 70%, energy and limestone resources can be saved, and CO can be reduced2Discharging(ii) a Meanwhile, a large amount of industrial solid wastes such as slag, fly ash and furnace bottom slag can be consumed, the environment is protected, and the cement production cost is reduced; the preparation method is simple, easy to operate and implement and convenient for realizing industrial application.
Description
Technical Field
The invention relates to the technical field of cementing materials, in particular to composite cement with few silicate clinker components and a preparation method thereof.
Background
The development direction and trend of the general portland cement are less clinker, multi-component, low cost, green, environment-friendly and low carbon. The composite cement with few silicate clinker components (hereinafter referred to as the clinker-less cement) is a low-carbon environment-friendly green product with few clinker components, which is developed and developed by adopting alkali-activated cementing materials and a geochemical mineral polymer technology according to the cement hydration, condensation and hardening theory, can improve the early and later strength of the cement in a balanced manner, reduce the water demand of the cement, improve the workability of the cement, improve the compactness of the cement concrete, save energy and limestone resources, reduce energy consumption and reduce carbon dioxide emission. Particularly has obvious advantages in greatly reducing the component content of cement clinker and the production cost of cement and realizing low carbon, green and environmental protection.
At present, the common portland cement which is largely applied to constructional engineering has high content of portland cement clinker components, which is approximately more than 50 percent, and the total amount of the admixture components of slag, fly ash, pozzolanic ash and the like and limestone and the like is less than 45 percent, and belongs to portland mineral-based cement. The production of ordinary Portland cement consumes a large amount of energy and limestone resources, and discharges a large amount of CO2And SO2、NOXAnd the like, causing environmental pollution. The cement of the common silicate cement has high hydration heat, cement concrete can generate large shrinkage and is easy to crack, the elastic modulus is low, the fireproof performance and the heat resistance are poor, and the corrosion resistance is poor. If the workability, cohesiveness, water retention property and other workability of the ordinary portland cement can meet the requirements of concrete construction performance, the workability can be realized only by adding corresponding chemical additives for adjustment.
Therefore, the technical workers in the field are dedicated to develop the composite cement with less silicate clinker components, which can save energy and limestone resources and reduce CO2And the product and the preparation technology belong to low-carbon environment-friendly green products and preparation technologies.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the composite cement with less silicate clinker components and the preparation method thereof, which can solve the defects of the prior ordinary silicate cement product and the preparation method thereof, and the obtained less silicate clinker componentsThe silicate clinker in the silicate clinker component composite cement has less consumption of silicate cement clinker, can save energy and limestone resources, and reduce CO2The discharge greatly consumes industrial solid wastes, and reduces the cement production cost; the preparation method is simple, easy to operate and implement and convenient for realizing industrial application.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
The composite cement with less silicate clinker components comprises the following preparation raw materials: portland cement clinker, gypsum, slag powder, fly ash, limestone powder and aluminosilicate mineral powder.
Preferably, the raw material further comprises a binder.
Further preferably, the binder comprises an alkali metal salt or/and an alkaline earth metal salt.
Further preferably, the alkali metal salt comprises one or more of sodium sulfate and sodium acetate.
Further preferably, the alkaline earth metal salt comprises one or more of sodium silicate and calcium formate.
Preferably, the aluminosilicate mineral powder comprises one or more of lead zinc tailings powder, copper tailings powder, iron tailings powder or basalt powder.
Preferably, the raw materials are used in the following amounts: 5-35% of portland cement clinker and gypsum, 20-30% of slag powder, 15-25% of fly ash, 20-25% of limestone powder and 10-15% of aluminosilicate mineral powder.
Further preferably, the mass ratio of the portland cement clinker to the gypsum is 5-30: 2-5.
Preferably, the portland cement clinker comprises: 3CaO SiO245 to 55 percent of mineral, 2CaO SiO212 to 20 percent of mineral, 3CaO and Al2O34.5 to 7.5 percent of mineral, 4CaO and Al2O3·Fe2O311 to 15 percent of mineral, 0.2 to 1.2 percent of free calcium oxide mineral and the balance of trace mineral.
As preferredWherein the gypsum comprises: CaSO4·2H2The content of O is not less than 85 percent, and the content of crystal water is not less than 14 percent.
Preferably, the slag powder has an activity index of not less than 95% and above of S95 grade and above.
Preferably, the loss on ignition of the fly ash is not higher than 8%, the screen residue of a 0.045mm square-hole sieve is not higher than 30%, and the activity index of the fly ash is not lower than 65%.
Preferably, in the limestone powder, Al2O3The content is less than or equal to 2.5 percent, and the CaO content is more than or equal to 48 percent.
Preferably, SiO is contained in the aluminosilicate mineral powder2Content is more than or equal to 45 percent, and Al2O3Content is less than or equal to 25 percent, Na2O+0.658K2O≤3.0％。
Preferably, the dosage of the binder accounts for 2-4% of the total mass of the silicate clinker-less component composite cement.
Further preferably, the mass ratio of the alkali metal salt to the alkaline earth metal salt is 1: 1.
(II) a preparation method of the composite cement with less silicate clinker components, which comprises the following steps:
step 1, mixing and grinding the portland cement clinker and the gypsum to a specific surface area of 350-2Per kg of the obtained material A;
drying and grinding the granulated blast furnace water-quenched slag to the specific surface area of 400-2Per kg of the obtained material B;
taking the residue of the fly ash with a 0.045mm sieve of which the sieve residue is not higher than 30 percent as a material C;
grinding limestone to a specific surface area of 400-450m2Per kg of the obtained material D;
grinding the aluminosilicate-based mineral powder to a specific surface area of 400-420m2Per kg of the obtained material E;
mixing and grinding the binder to a specific surface area of 200-300m2Per kg of the obtained material F;
and 2, mixing the materials A, B, C, D, E, F obtained in the step 1 to obtain the composite cement with less silicate clinker components.
Compared with the prior art, the invention has the beneficial effects that:
1) the silicate clinker consumption in the composite cement with less silicate clinker components is less, the clinker components can be as low as about 30 percent, the total mixing amount of mixed material components such as slag, fly ash, pozzolana, industrial solid waste, limestone and the like can be as high as about 70 percent, energy and limestone resources can be saved, and CO is reduced2Discharging; meanwhile, a large amount of industrial solid wastes such as slag, fly ash and furnace bottom slag can be consumed, and the environment is protected.
2) The composite cement with less silicate clinker components and concrete have good construction workability such as fluidity, cohesiveness, water retention and the like; the cement hydration heat is low, and the cement concrete is not easy to crack; the preparation method can reduce the production cost of cement, realize the development of low-carbon environment-friendly green products and technologies, and the obtained composite cement with few silicate clinker components can be applied to projects such as concrete, building walls, plastering, terraces, decoration and the like.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
The composite cement with less silicate clinker components comprises the following preparation raw materials in percentage by weight:
20% of portland cement clinker and gypsum, 30% of slag powder (granulated blast furnace water-quenched slag), 20% of fly ash, 20% of limestone powder and 10% of aluminosilicate-based mineral powder (containing solid waste). In addition, the alkali metal salt and alkaline earth metal salt binder account for 4% of the total mass of the composite cement containing less silicate clinker components, i.e. the total mass of the alkali metal salt and alkaline earth metal salt binder accounts for 4% of the total mass of silicate clinker, gypsum, slag powder, fly ash, limestone powder and aluminosilicate-based mineral powder.
Wherein the mass ratio of the portland cement clinker to the gypsum is 4: 1. In the portland cement clinker: 3CaO SiO2The mineral content is 55%，2CaO·SiO2Mineral content 20%, 3CaO & Al2O3Mineral content 7.0%, 4 CaO. Al2O3·Fe2O315% of minerals, 1.0% of free calcium oxide minerals and 2% of other trace minerals. CaSO in Gypsum Fibrosum4·2H2The percentage of O is not less than 86 percent, and the percentage of crystal water in gypsum is 14 percent. The slag powder is S95 grade, and the activity index is 97%. 6 percent of loss on ignition of the fly ash, 25 percent of residue on a 0.045mm sieve and 66 percent of activity index. Al in limestone powder2O32.0 percent of CaO and 49 percent of CaO. The aluminosilicate-based mineral powder (containing solid wastes) is iron tailing powder, SiO thereof265% of Al2O318% in content, alkali content (Na)2O+0.658K2O) was 1.8%. The alkali metal salt comprises sodium sulfate and sodium acetate, and the alkaline earth metal salt comprises sodium silicate and calcium formate; sodium sulfate: calcium formate: sodium acetate: sodium silicate 2:1:0.5: 2.
The preparation method of the composite cement with less silicate clinker components comprises the following steps:
step 1, mixing and grinding portland cement clinker and gypsum to reach a specific surface area of 350m2Per kg of the obtained material A; drying and grinding the granulated blast furnace water-quenched slag to 400m of specific surface area2Per kg of the obtained material B; the residue of 25 percent of the fly ash which is sieved by a 0.045mm square-hole sieve is material C; grinding limestone to 400m of specific surface area2Per kg of the obtained material D; grinding aluminosilicate-based mineral (containing solid waste) to 400m of specific surface area2Per kg of the obtained material E; mixing and grinding alkali metal salt and alkaline earth metal salt to specific surface area of 200m2Kg of material F.
And 2, mixing the materials A, B, C, D, E, F obtained in the step 1 to obtain the composite cement with less silicate clinker components.
Example 2
The composite cement with less silicate clinker components comprises the following preparation raw materials in percentage by weight:
25% of portland cement clinker and gypsum, 25% of slag powder, 17% of fly ash, 21% of limestone powder and 12% of aluminosilicate-based mineral powder (containing solid waste). In addition, the alkali metal salt and alkaline earth metal salt binder account for 3% of the total mass of the composite cement containing less silicate clinker components, i.e. the total mass of the alkali metal salt and alkaline earth metal salt binder accounts for 3% of the total mass of the silicate clinker, gypsum, slag powder, fly ash, limestone powder and aluminosilicate-based mineral powder.
Wherein the mass ratio of the portland cement clinker to the gypsum is 4: 1. In the portland cement clinker: 3CaO SiO255% of mineral, 2CaO SiO2Mineral content 20%, 3CaO & Al2O3Mineral content 7.5%, 4 CaO. Al2O3·Fe2O315% of minerals, 1.2% of free calcium oxide minerals and 1.3% of other trace minerals. CaSO in Gypsum Fibrosum4·2H2The content of O is not less than 87 percent, and the content of crystal water in gypsum is 16 percent. The slag powder is S95 grade, and the activity index is 98%. 5 percent of loss on ignition of the fly ash, 27 percent of residue on a 0.045mm square-hole sieve and 67 percent of activity index. Limestone powder Al2O31.8 percent of CaO and 50 percent of CaO. The aluminosilicate-based mineral powder (containing solid wastes) is basalt powder, SiO thereof2Content 63% of Al2O316% in content, alkali content (Na)2O+0.658K2O) was 1.4%. The alkali metal salt comprises sodium sulfate and sodium acetate, and the alkaline earth metal salt comprises sodium silicate and calcium formate; sodium sulfate: calcium formate: sodium acetate: sodium silicate 2:1:0.5: 2.
The preparation method of the composite cement with less silicate clinker components comprises the following steps:
step 1, mixing and grinding portland cement clinker and gypsum to specific surface area of 365m2Per kg of the obtained material A;
drying and grinding the granulated blast furnace water-quenched slag to the specific surface area of 410m2Per kg of the obtained material B;
the residue on the fly ash sieve with 0.045mm square holes is 27 percent, and the residue is a material C;
grinding limestone to specific surface area of 420m2Per kg of the obtained material D;
grinding aluminosilicate-based mineral (containing solid waste) to specific surface area of 415m2Per kg of the obtained material E;
mixing and grinding alkali metal salt and alkaline earth metal saltIs as thin as 260m of specific surface area2Kg of material F.
And 2, mixing the materials A, B, C, D, E, F obtained in the step 1 to obtain the composite cement with less silicate clinker components.
Example 3
The composite cement with less silicate clinker components comprises the following preparation raw materials in percentage by weight:
12% of portland cement clinker and gypsum, 30% of slag powder, 25% of fly ash, 22% of limestone powder and 11% of aluminosilicate-based mineral powder (containing solid waste). In addition, the alkali metal salt and alkaline earth metal salt binder account for 2.5% of the total mass of the composite cement containing less silicate clinker components, namely the total mass of the alkali metal salt and alkaline earth metal salt binder accounts for 2.5% of the total mass of the silicate clinker, gypsum, slag powder, fly ash, limestone powder and aluminosilicate-based mineral powder.
Wherein the mass ratio of the portland cement clinker to the gypsum is 2: 1. In the portland cement clinker: 3CaO SiO255% of mineral, 2CaO SiO2Mineral content 20%, 3CaO & Al2O3Mineral content 7.0%, 4 CaO. Al2O3·Fe2O315% of minerals, 1.0% of free calcium oxide minerals and 2% of other trace minerals. CaSO in Gypsum Fibrosum4·2H2The percentage of O is not less than 88 percent, and the percentage of crystal water in gypsum is 15 percent. The slag powder is S95 grade, and the activity index is 98%. 6 percent of loss on ignition of the fly ash, 25 percent of residue on a 0.045mm square-hole sieve and 68 percent of activity index. Limestone powder Al2O32.0 percent of CaO and 49 percent of CaO. The aluminosilicate-based mineral powder (containing solid wastes) is basalt powder, SiO thereof261% of Al2O3Content 21%, alkali content (Na)2O+0.658K2O) was 1.8%. The alkali metal salt is sodium sulfate, the alkaline earth metal salt is calcium formate, and the mass ratio of the sodium sulfate to the calcium formate is 1: 1.
The preparation method of the composite cement with less silicate clinker components comprises the following steps:
step 1, mixing and grinding portland cement clinker and gypsum to specific surface area of 370m2Per kg of the obtained material A;
drying and grinding the granulated blast furnace water-quenched slag to 408m of specific surface area2Per kg of the obtained material B;
28 percent of residual sieve of the 0.045mm square-hole sieve of the fly ash is taken as a material C;
grinding limestone to specific surface area of 450m2Per kg of the obtained material D;
grinding aluminosilicate-based mineral (containing solid waste) to specific surface area of 420m2Per kg of the obtained material E;
mixing and grinding alkali metal salt and alkaline earth metal salt to specific surface area of 300m2Per kg of the obtained material F;
and 2, mixing A, B, C, D, E, F to obtain the composite cement with less silicate clinker components.
In the above embodiment, the granulated blast furnace slag in the raw material for preparing the composite cement with less silicate clinker components can improve the cohesiveness of the cement, and improve the later strength of the cement and the compactness of a concrete structure; the fly ash can reduce the water demand of cement and concrete and improve the working performance of the cement and the concrete; the pozzolanic material such as basalt powder and the like can improve the water retention performance of cement and concrete; the limestone can improve the early strength of the cement and prevent the concrete from bleeding. The composite cement with less silicate clinker components, which is obtained by the invention, has more obvious advantages and is more environment-friendly when being applied to the aspects of building wall building, plastering, terrace, decoration and the like. The composite cement with less silicate clinker components prepared by blending the content and the grain composition of the cement components and adopting a new cement technology and the like can better meet the special performance requirements of concrete. The composite cement containing less silicate clinker components and the multi-component mixed material have more outstanding advantages in the aspects of improving and controlling the performance of cement and concrete.
The detection standard and method of the relevant performance of the above embodiment are as follows:
the indexes of 0.045mm square hole sieve residue, specific surface area, standard consistency water requirement, setting time, activity index, fluidity and the like of the composite cement with less silicate clinker components obtained in the examples 1 to 3 are tested by referring to standard test methods such as a clean slurry fluidity method (substitution method) in GB/T18046-2017 granulated blast furnace slag powder used in cement, mortar and concrete, GB/T1345-2005 cement fineness test method analysis method, GB/T1346 cement standard consistency water consumption, setting time and stability test method in GB/T1346 cement compatibility test method, and the test results are shown in tables 1-2.
The composite cement with less silicate clinker components obtained in the examples 1 to 3 was subjected to a compressive strength test with reference to national standard GB/T1596-2017 fly ash for cement and concrete and GB/T17671-1999 Cement mortar Strength test method (ISO method), and the test results are shown in Table 2. In tables 1-2, comparative example 1 is commercially available M32.5 masonry cement.
TABLE 1 control index test result table for composite cement containing less silicate clinker components
As seen from Table 1, the composite cement with less silicate clinker components of examples 1-3 has indexes of specific surface area and screen residue, etc. meeting the cement performance index requirement in JC/T1083-2008 & lt & lttest method for compatibility of cement and admixture & gt, and the water requirement for standard consistency is obviously reduced compared with the comparative example 1.
TABLE 2 table of the test results of various quality indexes of the composite cement containing less silicate clinker components
As seen from Table 2, the low silicate clinker component composite cements of examples 1-3 have significantly improved water retention, significantly higher compressive strength at each age than the same class of conventional cements, better rheology, better workability of cement, and better compatibility with additives, as compared to comparative example 1.
The composite cement with less silicate clinker components has more outstanding advantages in the aspects of saving energy and resources, improving and regulating the performance of cement and concrete, and specifically comprises the following components: (1) silicate ripeningThe material consumption is less, the energy and limestone resources can be saved, and the CO can be reduced2And (5) discharging. (2) The industrial solid wastes such as slag, fly ash and furnace bottom slag can be greatly absorbed, and the environment is protected; (3) the cohesive property of the cement can be improved, and the later strength of the cement and the compactness of a concrete structure are improved; (4) the water demand of cement and concrete can be reduced, and the working performance of the cement and the concrete can be improved; (5) the water retention performance of cement and concrete can be improved; (6) the early strength of the cement can be improved, and the concrete bleeding can be prevented; (7) can reduce the production cost of cement and realize the development of low-carbon environment-friendly green products and technologies.
The composite cement with less silicate clinker components can save energy and limestone resources, reduce energy consumption and reduce carbon dioxide emission. The early and later strength of the cement is improved in a balanced manner, the water demand of the cement is reduced, the workability of the cement is improved, and the compactness of the concrete is improved. Particularly has obvious advantages in greatly reducing the component content of portland cement clinker and the production cost of cement and realizing low carbon, green and environmental protection, and belongs to a green and environmental-friendly low carbon product and technology.
Although the present invention has been described in detail in this specification with reference to specific embodiments and illustrative embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The composite cement with few silicate clinker components is characterized by comprising the following preparation raw materials: portland cement clinker, gypsum, slag powder, fly ash, limestone powder and aluminosilicate mineral powder.
2. The low silicate clinker component composite cement of claim 1, wherein the raw materials further comprise a binder.
3. The low silicate clinker component composite cement of claim 2, wherein the binder comprises an alkali metal salt or/and an alkaline earth metal salt.
4. The low silicate clinker component composite cement of claim 3, wherein the alkali metal salt comprises one or more of sodium sulfate, sodium acetate; the alkaline earth metal salt comprises one or more of sodium silicate and calcium formate.
5. The low silicate clinker component composite cement of claim 1, wherein the aluminosilicate mineral powder comprises one or more of lead zinc tailings powder, copper tailings powder, iron tailings powder, or basalt powder.
6. The low silicate clinker component composite cement of claim 1, wherein the raw materials are used in amounts of: 5-35% of portland cement clinker and gypsum, 20-30% of slag powder, 15-25% of fly ash, 20-25% of limestone powder and 10-15% of aluminosilicate mineral powder; wherein the mass ratio of the portland cement clinker to the gypsum is 5-30: 2-5.
7. The low portland clinker component composite cement of claim 6, wherein the portland cement clinker comprises: 3CaO SiO245 to 55 percent of mineral, 2CaO SiO212 to 20 percent of mineral, 3CaO and Al2O34.5 to 7.5 percent of mineral, 4CaO and Al2O3·Fe2O311 to 15 percent of mineral, 0.2 to 1.2 percent of free calcium oxide mineral and the balance of trace mineral; the gypsum comprises: CaSO4·2H2The content of O is not less than 85 percent, and the content of crystal water is not less than 14 percent.
8. The low silicate clinker component composite cement of claim 6, wherein the loss on ignition of the fly ash is not higher than 8%, the screen residue of a 0.045mm square mesh screen is not higher than 30%, and the activity index of the fly ash is not lower than 65%; the limestoneIn powder, Al2O3The content is less than or equal to 2.5 percent, and the CaO content is more than or equal to 48 percent; in the aluminosilicate mineral powder, SiO2Content is more than or equal to 45 percent, and Al2O3Content is less than or equal to 25 percent, Na2O+0.658K2O≤3.0％。
9. The low silicate clinker component composite cement as claimed in claim 2, wherein the amount of the binder is 2-4% of the total mass of the low silicate clinker component composite cement.
10. The preparation method of the composite cement with few silicate clinker components is characterized by comprising the following steps:
step 1, mixing and grinding the portland cement clinker and the gypsum to a specific surface area of 350-2Per kg of the obtained material A;
drying and grinding the granulated blast furnace water-quenched slag to the specific surface area of 400-2Per kg of the obtained material B;
taking the residue of the fly ash with a 0.045mm sieve of which the sieve residue is not higher than 30 percent as a material C;
grinding limestone to a specific surface area of 400-450m2Per kg of the obtained material D;
grinding the aluminosilicate-based mineral powder to a specific surface area of 400-420m2Per kg of the obtained material E;
mixing and grinding the binder to a specific surface area of 200-300m2Per kg of the obtained material F;
and 2, mixing the materials A, B, C, D, E, F obtained in the step 1 to obtain the composite cement with less silicate clinker components.
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