CN117700189A - High-performance solid waste-based cementing material and preparation method thereof - Google Patents
High-performance solid waste-based cementing material and preparation method thereof Download PDFInfo
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- 239000002910 solid waste Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title description 6
- 239000002893 slag Substances 0.000 claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 48
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 46
- 239000010959 steel Substances 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 32
- 239000004568 cement Substances 0.000 claims abstract description 32
- 239000010440 gypsum Substances 0.000 claims abstract description 23
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 239000012190 activator Substances 0.000 claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000001110 calcium chloride Substances 0.000 claims abstract description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 7
- 235000011187 glycerol Nutrition 0.000 claims abstract description 6
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims abstract description 6
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims abstract description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940043276 diisopropanolamine Drugs 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims description 20
- 239000000292 calcium oxide Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 23
- 238000006703 hydration reaction Methods 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 13
- 230000036571 hydration Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 229910001653 ettringite Inorganic materials 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000005284 excitation Effects 0.000 description 7
- 239000011398 Portland cement Substances 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- -1 silicon aluminum sulfur calcium Chemical compound 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a high-performance solid waste-based cementing material, which comprises the following components in parts by weight: 40-60 parts of slag powder, 15-30 parts of steel slag powder, 5-15 parts of desulfurized gypsum, 5-15 parts of cement clinker, 3-5 parts of calcination auxiliary agent and 1-3 parts of chemical activator; the calcining auxiliary agent is obtained by compounding sodium chloride, calcium chloride and sodium silicate; the chemical activator is compounded with anhydrous sodium sulfate, sodium thiocyanate, sodium methylbenzenesulfonate, ethanol diisopropanolamine and polymerized glycerin. The invention can realize the resource utilization of various solid wastes such as steel slag, desulfurized gypsum, construction waste and the like, simultaneously effectively give consideration to the properties such as good early strength, good later strength and the like, effectively widen the application range of the solid waste base cementing material, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a high-performance solid waste-based cementing material and a preparation method thereof.
Background
Carbon emissions in cement production come mainly from three aspects, namely carbonate raw material decomposition carry-over (process emissions), fuel combustion carry-over (combustion emissions) and production facility power consumption (indirect emissions). At present, the main measures of reducing carbon in the cement industry are to reduce the dosage of cement clinker production, improve the cement proportion with low clinker content and improve the dosage of novel low-carbon cementing materials.
The utilization rate of other solid wastes such as steel slag, desulfurized ash and the like in the current metallurgical waste slag of the steel enterprise is lower, and the recycling utilization of a large amount of solid wastes is still an important problem which puzzles the sustainable development of the main industry of the steel enterprise. In the steel production process, various solid wastes such as slag, steel slag, circulating ash, furnace slag, low-grade fly ash, construction waste, iron tailings, stone dust and the like are generated. Besides slag, the utilization rate of a large amount of solid wastes is low, the production added value is low, and the burden which puzzles the development of the industry is gradually formed. Therefore, the method is an urgent task for the development of enterprises to properly treat the solid waste generated by metallurgical enterprises and apply the solid waste to products with higher added values.
At present, a certain research on recycling of solid wastes is carried out, such as: patent CN115572084a discloses a multi-steel slag synergistic solid waste-based cementing material and a preparation method thereof; patent CN115893896a provides a solid waste-based concrete composite mineral admixture. However, the solid waste-based cementing material obtained by the scheme still has the problems of low early strength, low upper limit of later strength and the like, and the popularization and application of the solid waste-based cementing material are limited to a certain extent.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention provides the high-performance solid waste-based cementing material, which can realize the resource utilization of the solid wastes such as steel slag, desulfurized gypsum, construction waste and the like, and simultaneously can realize good early strength, later strength and the like, thereby effectively widening the application range of the solid waste-based cementing material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the high-performance solid waste-based cementing material comprises the following components in parts by weight: 40-60 parts of slag powder, 15-30 parts of steel slag powder, 5-15 parts of desulfurized gypsum, 5-15 parts of cement clinker, 3-5 parts of calcination auxiliary agent and 1-3 parts of chemical activator; the calcining auxiliary agent is obtained by compounding sodium chloride, calcium chloride and sodium silicate; the chemical activator is compounded with anhydrous sodium sulfate, sodium thiocyanate, sodium methylbenzenesulfonate, ethanol diisopropanolamine and polymerized glycerin.
According to the scheme, the slag powder comprises the following main chemical components in percentage by mass: siO (SiO) 2 30～35％，CaO 35～40％，Al 2 O 3 8～20％，Fe 2 O 3 0.1～2％，MgO 6～12％，SO 3 2 to 5 percent of the slag powder is ground to reach the activity requirement of mineral powder with the S95 grade above in national standard, and the specific surface area is 400 to 420m 2 /kg。
Further, the slag may be water slag or the like.
According to the scheme, the steel slag powder comprises the following main chemical components in percentage by mass: siO (SiO) 2 15～25％，CaO 30～40％，Al 2 O 3 3～8％，Fe 2 O 3 10～25％，MgO 10～15％，SO 3 0.2-2% and loss on ignition less than or equal to 8%; specific surface area of 300-350 m 2 /kg。
Further, the steel slag powder is obtained by grinding steel slag by adopting a roller press.
According to the scheme, the main chemical components in the desulfurized gypsum comprise the following components in percentage by mass: 25-29% of CaO and SO 3 42-48% and loss on ignition of 20-30%.
Further, the desulfurization gypsum is pre-dried under the condition of 170 ℃ until the water content is about 8-12%.
According to the scheme, the cement clinker comprises the following main chemical components in percentage by mass: siO (SiO) 2 20～24％，CaO 60～67％，Al 2 O 3 3～8％，Fe 2 O 3 2.5 to 8 percent; the specific surface area is 380-420 m 2 /kg。
According to the scheme, the calcination auxiliary agent comprises (10-15)/(4-8)/(2-4) by mass ratio of sodium chloride, calcium chloride and sodium silicate, and has the function of helping to reduce the melting point of mineralsCan promote the adhesion of calcium chloride and sodium silicate in liquid phase to C under high temperature melting state 2 S surface for promoting steel slag powder C 2 And S and the like, and further improves the early strength of the mineral phase.
According to the scheme, in the chemical activator, the mass ratio of anhydrous sodium sulphate to sodium thiocyanate to sodium methylbenzenesulfonate to ethanol diisopropanolamine to polymerized glycerol is (3-8): (4-6): (0.2-0.6): (0.3-0.8): (0.1-0.5), and the chemical activator has the functions of grinding assistance and hydration activity excitation.
The preparation method of the high-performance solid waste-based cementing material comprises the following steps:
1) Weighing steel slag powder and desulfurized gypsum according to the proportion, and simultaneously ensuring that the chemical composition of the obtained mixture I meets the following conditions: siO (SiO) 2 10～20％、CaO 30～35％、Al 2 O 3 3～7％、Fe 2 O 3 1.5～3％、SO 3 10-20% and loss on ignition less than or equal to 2.5%;
2) Adding a calcining auxiliary agent into the obtained mixture I, and calcining at a high temperature;
3) Mixing the calcined material obtained in the step 2) with the weighed slag powder and cement clinker, adding a chemical activating agent, and grinding until the specific surface area is 450m 2 And (3) above kg, obtaining the high-performance solid waste-based cementing material.
In the scheme, the high-temperature calcination temperature is 700-750 ℃, and the high-temperature retention time is 20-30 s.
The high-performance solid waste-based cementing material is prepared by compounding high-activity slag and low-activity solid waste in a steel plant, blending a small amount of clinker and chemical reagents, and utilizing the means of mechanical grinding activation, combined calcination, synergistic excitation among components, excitation by an external activator and the like, wherein the strength of the high-performance solid waste-based cementing material can reach P.O 42.5.42.5 cement strength grade, and the strength of the high-performance solid waste-based cementing material can reach P.I 52.5.5 cement strength grade.
The principle of the invention is as follows:
the solid waste-based cementing material can form needle-shaped ettringite, flocculent C-S-H gel and flaky Ca (OH) in the early hydration process 2 The main product is: early hydration of cement clinker to form aluminum hydrateCalcium acid, and produces a large amount of Ca (OH) 2 The steel slag contains a large amount of oxide, after thermal activation and calcination, the alkalinity is enhanced, and the chemical activator is alkaline, which can lead to OH - The concentration is increased to precipitate crystals, so that the crystals continuously react with active silicon oxide, aluminum oxide and sulfate ions in the mineral powder to generate ettringite, C-S-H gel and the like (namely alkali excitation); the invention adopts the steel slag powder and the desulfurized gypsum to be calcined together under the condition of calcining auxiliary agent, can promote the desulfurized gypsum to be transformed into betse:Sup>A-type gypsum, can effectively excite the activities of silicon oxide, aluminum oxide and the like in the steel slag powder, and enables the steel slag powder to form an S-C-S-A system (se:Sup>A silicon aluminum sulfur calcium coupling system), and the rate of forming ettringite to be doubled in the early hydration process, thereby obviously improving the early strength. As the hydration reaction proceeds, the Ca (OH) flakes in the late hydration product 2 Gradually decreasing but ettringite and C-S-H gels significantly increase. This is because as the hydration reaction proceeds, the ultrafine slag powder (secondary hydration) and the steel slag powder (C formed after calcination 2 S) the potential activity of the catalyst is slowly excited, the amount of calcium hydroxide is continuously consumed, ettringite is formed in the system and is taken as a framework, C-S-H gel and other hydration products are filled in the framework and pores, so that the structure is more compact, and the macroscopic mechanical property is obviously improved. In addition, the superfine grinding process adopted by the invention can effectively increase the contact area with water in the hydration process, has more remarkable effect under the condition of low water-gel ratio, can fill most of gaps, reduces free water required for maintaining the workability of slurry, and effectively improves the strength of concrete.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention firstly utilizes the desulfurized gypsum and the steel slag powder to carry out mixed pre-calcination under the condition of calcining auxiliary agent, and utilizes the sulfate radical ion of the desulfurized gypsum and the calcining auxiliary agent to reduce the melting point of partial minerals of the steel slag powder, thereby effectively eliminating the instability problem of free calcium oxide and magnesium oxide, and on the other hand, the invention can dissolve partial minerals with compact crystallization and coarse grains in the steel slag powder to form more C 3 S、C 2 S and other minerals, increase the activity of steel slag powder, form a silicon-aluminum-sulfur-calcium coupling system, and can effectivelyImproving early strength, etc.;
2) The calcined material (gypsum-steel slag powder) obtained by calcination is further ground in combination with slag powder and cement clinker, so that the effects of alkali excitation and sulfate excitation can be further exerted, and the early strength, the later strength and the like of the obtained concrete are effectively considered.
Drawings
FIG. 1 is an SEM image of hydrated 3d of a sample of cement paste obtained in comparative example 1; wherein (a) the scale is 200nm and (b) the scale is 1 μm;
FIG. 2 is an SEM image of hydrated 3d of a sample of the cement paste obtained in comparative example 2; wherein (a) the scale is 200nm and (b) the scale is 1 μm;
FIG. 3 is an SEM image of hydrated 3d of a sample of the cement paste obtained in example 3; wherein (a) the scale is 200nm and (b) the scale is 1 μm;
FIG. 4 is an SEM image of hydrated 3d of a sample of the cement paste obtained in example 4; wherein (a) the scale is 200nm and (b) the scale is 1 μm;
FIG. 5 is an SEM image of hydration 28d of the cement paste sample obtained in comparative example 1; wherein (a) the scale is 1 μm and (b) the scale is 2 μm;
FIG. 6 is an SEM image of hydration 28d of the cementitious slurry sample of comparative example 2; wherein (a) the scale is 1 μm and (b) the scale is 2 μm;
FIG. 7 is an SEM image of hydration 28d of a cementitious slurry sample as obtained in example 3; wherein (a) the scale is 1 μm and (b) the scale is 2 μm;
FIG. 8 is an SEM image of hydration 28d of a cementitious slurry sample as obtained in example 4; wherein (a) the scale is 1 μm and (b) the scale is 2 μm.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further, but are not to be construed as limiting the present invention.
The slag powder, steel slag powder, desulfurized gypsum, cement clinker, calcination auxiliary agent and chemical activator adopted in the specific embodiment are composed of the following components in parts by weight: 40-60 parts of slag, 15-30 parts of steel slag, 5-15 parts of desulfurized gypsum, 5-15 parts of cement clinker, 3-5 parts of calcination auxiliary agent and 1-3 parts of chemical activating agent;
the following are the followingIn the embodiment, the slag is byproduct water slag after water quenching of the blast furnace iron making of the armed steel, and the main chemical components and the weight percentages thereof comprise: siO (SiO) 2 30～35％、CaO 35～40％、Al 2 O 3 8～20％、Fe 2 O 3 0.1～2％、MgO 6～12％、SO 3 2-5%, and the activity requirement of more than S95 grade in national standard is achieved after grinding.
The adopted steel slag is provided by Bao Wu Huanke metal company, and the main chemical components and the weight percentages thereof are as follows: siO (SiO) 2 15～25％、CaO 30～40％、Al 2 O 3 3～8％、Fe 2 O 3 10～25％、MgO 10～15％、SO 3 0.2-2% and loss on ignition less than or equal to 8%.
The adopted undisturbed desulfurization gypsum is provided by Qingshan power plant, and comprises the following main chemical components in percentage by weight: 25-29% of CaO and SO 3 42-48% and loss on ignition of 20-30%.
The adopted cement clinker is provided by Hubei Dazhiyuan peak cement, and comprises the following main chemical components in percentage by weight: siO (SiO) 2 20～24％、CaO 60～67％、Al 2 O 3 3～8％、Fe 2 O 3 2.5～8％。
The adopted calcination auxiliary agent is prepared by mixing (10-15): (4-8): (2-4) by mass ratio of sodium chloride, calcium chloride and sodium silicate, and has the function of reducing the melting point of minerals, and the ratio of the calcination auxiliary agent in comparative example 1 to the calcination auxiliary agent in examples 1-8 is 10:6:4.
The chemical activator is prepared from anhydrous sodium sulfate: sodium thiocyanate: sodium methyl benzenesulfonate: ethanol and isopropanolamine: the polymerized glycerin is mixed according to the mass ratio of (3-8): (4-6): (0.2-0.6): (0.3-0.8): (0.1-0.5), and has the functions of grinding assistance and hydration activity excitation, and the proportion of chemical activators in the comparative example and the examples is as follows: 5:5:0.5:0.4:0.3.
Examples 1 to 5
The specific preparation process of the high-performance solid waste-based cementing material described in examples 1 to 5 is as follows:
1) Grinding the steel slag by a roller press to obtain the steel slag with the specific surface area of 300m 2 /kg, steel slag powder above;
2) Pre-drying the undisturbed desulfurized gypsum at 170 ℃ to ensure that the moisture content is between 8 and 12 percent;
3) Proportioning the products obtained in 1) and 2) according to the proportion, and simultaneously ensuring that the chemical composition requirements of the obtained mixture are satisfied: siO (SiO) 2 12～17％、CaO 31～33％、Al 2 O 3 3～5％、Fe 2 O 3 11～15％、SO 3 10-18% and loss on ignition less than or equal to 2.5%;
4) Adding a calcining auxiliary agent into the mixture obtained in the step 3), and calcining at a high temperature of 700 ℃ for 20s;
5) Grinding the water slag by a vertical mill to obtain the specific surface area 410m 2 Slag powder/kg;
6) The clinker is ground by a roller press to obtain the specific surface area 330m 2 Clinker powder/kg;
7) Mixing the powder obtained in the steps 4) to 6) into a ball mill according to a proportion (specifically shown in table 1), adding an exciting agent, and grinding until the specific surface area is 600m 2 And (3) Kg to obtain the high-performance solid waste-based cementing material.
Comparative example 1
The solid waste type cementing material is prepared by the following steps:
1) Grinding the steel slag by a roller press to obtain the steel slag with the specific surface area of 300m 2 Steel slag powder above/kg;
2) Pre-drying the undisturbed desulfurized gypsum at 170 ℃ to ensure that the moisture content is between 8 and 12 percent;
3) Grinding the water slag by a vertical mill to obtain the specific surface area 410m 2 Slag powder/kg;
4) The cement clinker is ground by a roller press to obtain a specific surface area of 330m 2 Cement clinker powder/kg;
5) Mixing the powder obtained in the steps 1) to 4) into a ball mill according to a proportion (specifically shown in the table 1), adding an exciting agent, and grinding until the specific surface area is 600m 2 And (3) per kg to obtain the solid waste-based cementing material of the comparative example 1.
Comparative example 2
The solid waste type cementing material is prepared by the following steps:
1) Grinding the steel slag by a roller press to obtain the steel slag with the specific surface area of 300m 2 Steel slag powder above/kg;
2) Pre-drying the undisturbed desulfurized gypsum at 170 ℃ to ensure that the moisture content is between 8 and 12 percent;
3) Proportioning the products obtained in 1) and 2) according to the proportion, and simultaneously ensuring that the chemical composition requirements of the obtained mixture are satisfied: siO (SiO) 2 12-17％、CaO 31～33％、Al 2 O 3 3～5％、Fe 2 O 3 11～15％、SO 3 8-20% and loss on ignition less than or equal to 2.5%;
4) Calcining the mixture obtained in the step 3) at a high temperature of 700 ℃ for 20s;
5) Grinding the water slag by a vertical mill to obtain the specific surface area 410m 2 Slag powder/kg;
6) The clinker is ground by a roller press to obtain the specific surface area 330m 2 Clinker powder/kg;
7) Mixing the powder obtained in the steps 4) to 6) into a ball mill according to the proportion (specifically shown in the table 1), and grinding to the specific surface area of 600m 2 And (3) per kg to obtain the solid waste-based cementing material.
Comparative example 3
The solid waste type cementing material is prepared by the following steps:
1) Grinding the steel slag by a roller press to obtain the steel slag with the specific surface area of 300m 2 Steel slag powder above/kg;
2) Pre-drying the undisturbed desulfurized gypsum at 170 ℃ to ensure that the moisture content is between 8 and 12 percent;
3) Proportioning the products obtained in 1) and 2) according to the proportion, and simultaneously ensuring that the chemical composition requirements of the obtained mixture are satisfied: siO (SiO) 2 12～17％、CaO 31～33％、Al 2 O 3 3～5％、Fe 2 O 3 11～15％、SO 3 10-18% and loss on ignition less than or equal to 2.5%;
4) Adding a calcining auxiliary agent with the mass ratio of calcium chloride to sodium chloride being 1:1 into the mixture obtained in the step 3), and calcining at a high temperature of 700 ℃ for 20s;
5) Grinding the water slag by a vertical mill to obtain the specific surface area 410m 2 Slag powder/kg;
6) The clinker is ground by a roller press to obtain the specific surface area 330m 2 Clinker powder/kg;
7) Mixing the powder obtained in the steps 4) to 6) into a ball mill according to the proportion (specifically shown in the table 1), and grinding to the specific surface area of 600m 2 And (3) per kg to obtain the solid waste-based cementing material.
Table 1 proportions (parts by weight) of the high-performance solid waste-based cementing materials according to comparative examples 1 to 2 and examples 1 to 5
| Examples | Slag (slag) | Steel slag | Clinker material | Desulfurized gypsum | Calcination aid | Activating agent |
| Comparative example 1 | 50 | 22 | 12 | 10 | 0 | 2 |
| Comparative example 2 | 50 | 22 | 12 | 10 | 0 | 2 |
| Comparative example 3 | 50 | 22 | 12 | 10 | 4 | 2 |
| Example 1 | 40 | 24 | 15 | 15 | 5 | 1 |
| Example 2 | 45 | 24 | 12 | 12 | 5 | 2 |
| Example 3 | 50 | 22 | 12 | 10 | 4 | 2 |
| Example 4 | 55 | 19 | 10 | 10 | 3 | 3 |
| Example 5 | 60 | 24 | 5 | 5 | 3 | 3 |
Table 2 comparative examples 1 to 2, compositions and specific surface areas of solid waste-based gelled materials described in examples 1 to 5
In table 2, the content of each chemical component is in parts by weight.
The high-performance solid waste-based cementing materials corresponding to the examples shown in table 1 are mixed with standard sand according to the weight ratio of 1:3 in sequence, and then the cement mortar is obtained according to the water-cement ratio of 0.5 or 0.45, and the specific performance test results are shown in tables 3 and 4. For comparison, pure portland cement (P.O 42.5.42.5) was formulated as a benchmark set S of cement.
TABLE 3 test results of the corresponding mortar intensities for examples, reference and control groups
Table 4 test results of the respective examples, reference group, control group for the strength of the sand
As can be seen from the data in Table 3, the 3d and 28d strengths of examples 1-5 both meet the technical requirements for the strength of P.O 42.5.5 cement in the GB/T175 general Portland Cement standard, and the product without calcination or addition of an activator does not meet the technical requirements for the strength of P.O 42.5.5 cement in the GB/T175 general Portland Cement standard, AS compared with the use of the pure Portland cement AS group.
As can be seen from the data in table 4, the 3d and 28d strengths of the cement mortars obtained in examples 1 to 5 are superior to those of the general Portland cement, compared with the standard group using pure Portland cement, which indicates that the effect of the high-strength high-performance solid waste-based cementing material is more remarkable under the condition of smaller water-cement ratio.
FIGS. 1 to 8 are SEM images of hydrated 3d and 28d of samples of cement paste (water-gel ratio: 0.28) obtained in comparative examples 1 to 3 and examples 3 to 4, respectively. As can be seen from the hydrated 3d SEM pictures, the samples obtained in comparative examples 1 and 2 had significantly less ettringite than the samples obtained in examples 3 and 4, and the comparative examples 1 and 2 also had more defects in the pores, which were shown to have lower 3d compressive strengths in strength than the samples of examples 3 and 4. The samples obtained in examples 3 and 4 showed no large difference in the number, size, pore size and the like of ettringite, and no large difference in 3d compressive strength. Moreover, it can be seen that ettringite of the samples obtained in examples 3 and 4 forms a more pronounced network structure, whereas comparative examples 1 and 2 are still in the initial stage of their network structure construction due to the slow rate of hydration reaction, which is why the compressive strength of comparative example 23d is lower than that of examples 3 and 4. As can be seen from the 28d SEM pictures, the hydrate structure of the samples obtained in examples 3 and 4 is much denser than the results of the hydrates of comparative examples 1 and 2, while the hydrates of comparative examples 1 and 2 still have more pore defects, which is shown by the 28d compressive strength of comparative example 2 being lower than the 28d compressive strength of the samples of examples 3 and 4. The strength of the cementing material obtained by the invention in each stage has obvious influence.
It is apparent that the above examples are only examples given for clarity of illustration and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And thus obvious variations or modifications to the disclosure are within the scope of the invention.
Claims (9)
1. The high-performance solid waste-based cementing material is characterized by comprising the following components in parts by weight: 40-60 parts of slag powder, 15-30 parts of steel slag powder, 5-15 parts of desulfurized gypsum, 5-15 parts of cement clinker, 3-5 parts of calcination auxiliary agent and 1-3 parts of chemical activator; the calcining auxiliary agent is obtained by compounding sodium chloride, calcium chloride and sodium silicate; the chemical activator is compounded with anhydrous sodium sulfate, sodium thiocyanate, sodium methylbenzenesulfonate, ethanol diisopropanolamine and polymerized glycerin.
2. The high-performance solid waste-based cementing material according to claim 1, wherein the slag powder comprises the following main chemical components in percentage by mass: siO (SiO) 2 30～35％，CaO 35～40％，Al 2 O 3 8～20％，Fe 2 O 3 0.1～2％，MgO 6～12％，SO 3 2-5% and the specific surface area is 400-420 m 2 /kg。
3. The high-performance solid waste-based cementing material according to claim 1, wherein the main chemical components in the steel slag powder and the mass percentages thereof comprise: siO (SiO) 2 15～25％，CaO 30～40％，Al 2 O 3 3～8％，Fe 2 O 3 10～25％，MgO 10～15％，SO 3 0.2-2% and loss on ignition less than or equal to 8%; specific surface area of 300-350 m 2 /kg。
4. The high-performance solid waste-based cementing material according to claim 1, wherein the main chemical components in the desulfurized gypsum and the mass percentages thereof comprise: caO 25-29%、SO 3 42-48% and loss on ignition of 20-30%.
5. The high-performance solid waste-based cementing material according to claim 1, wherein the main chemical components in the cement clinker and the mass percentages thereof comprise: siO (SiO) 2 20～24％，CaO 60～67％，Al 2 O 3 3～8％，Fe 2 O 3 2.5 to 8 percent; the specific surface area is 380-420 m 2 /kg。
6. The high-performance solid waste-based cementing material according to claim 1, wherein the mass ratio of sodium chloride, calcium chloride and sodium silicate in the calcination auxiliary agent is (10-15): 4-8): 2-4.
7. The high-performance solid waste-based cementing material according to claim 1, wherein the mass ratio of anhydrous sodium sulphate, sodium thiocyanate, sodium methylbenzenesulfonate, monoethanol diisopropanolamine and polymerized glycerol in the chemical activator is (3-8): 4-6): 0.2-0.6): 0.3-0.8): 0.1-0.5.
8. The method for preparing the high-performance solid waste-based cementing material according to any one of claims 1 to 7, which is characterized by comprising the following steps:
1) Weighing steel slag powder and desulfurized gypsum according to the proportion, and simultaneously ensuring that the chemical composition of the obtained mixture I meets the following conditions: siO (SiO) 2 10～20％、CaO 30～35％、Al 2 O 3 3～7％、Fe 2 O 3 1.5～3％、SO 3 10-20% and loss on ignition less than or equal to 2.5%;
2) Adding a calcining auxiliary agent into the obtained mixture I, and calcining at a high temperature;
3) Mixing the calcined material obtained in the step 2) with the weighed slag powder and cement clinker, adding a chemical activating agent, and grinding until the specific surface area is 450m 2 And (3) above kg, obtaining the high-performance solid waste-based cementing material.
9. The method according to claim 8, wherein the high-temperature calcination temperature is 700 to 750 ℃ for 20 to 30 seconds.
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