CN116395997A - Auxiliary cementing material and preparation method and application thereof - Google Patents
Auxiliary cementing material and preparation method and application thereof Download PDFInfo
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- CN116395997A CN116395997A CN202310448782.4A CN202310448782A CN116395997A CN 116395997 A CN116395997 A CN 116395997A CN 202310448782 A CN202310448782 A CN 202310448782A CN 116395997 A CN116395997 A CN 116395997A
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- micro powder
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- 239000000463 material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 108
- 239000004927 clay Substances 0.000 claims abstract description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 12
- 230000001089 mineralizing effect Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002689 soil Substances 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims abstract description 3
- 238000009736 wetting Methods 0.000 claims abstract description 3
- 239000004568 cement Substances 0.000 claims description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- 230000033558 biomineral tissue development Effects 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000013618 particulate matter Substances 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003469 silicate cement Substances 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 3
- 239000004567 concrete Substances 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 239000000404 calcium aluminium silicate Substances 0.000 description 5
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 5
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 5
- 229940078583 calcium aluminosilicate Drugs 0.000 description 5
- 229910052622 kaolinite Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- -1 aluminate ions Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JETSKDPKURDVNI-UHFFFAOYSA-N [C].[Ca] Chemical compound [C].[Ca] JETSKDPKURDVNI-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of municipal engineering and building materials, in particular to an auxiliary cementing material and a preparation method and application thereof. The auxiliary cementing material comprises flash clay and mineralized regenerated micro powder; the preparation method of the flash-burned clay comprises pulping engineering waste soil, press-filtering to obtain mud cake, sequentially wet-filtering, centrifuging, drying and grinding the mud cake to obtain clay powder, and calcining the clay powder; the preparation method of the mineralized and regenerated micro powder comprises the steps of mineralizing and regenerating micro powder by a semi-dry method, drying and grinding to obtain the mineralized and regenerated micro powder, wherein the semi-dry mineralized concrete steps comprise: spraying sodium hydroxide solution on the surface of the spread regenerated micro powder for wetting, and then mineralizing in an environment with the relative humidity of 80-100% RH. The auxiliary cementing material can replace ordinary silicate cement in a large proportion, and the preparation method has the advantages of low energy consumption, short time consumption and high efficiency.
Description
Technical Field
The invention relates to the technical field of municipal engineering and building materials, in particular to an auxiliary cementing material and a preparation method and application thereof.
Background
The continuous rapid increase of urban population leads to the increasing demand for residential and traffic infrastructure, and the annual generation of engineering waste of various buildings and municipal engineering in Shenzhen city is close to 1 million tons, so that the disposal and the digestion of engineering waste are becoming the bottleneck problem of building 'no waste city'. At present, the resource utilization of engineering waste soil is mostly to prepare building materials by taking cement or water glass as an adhesive and engineering waste soil as a filling material.
Besides a large amount of engineering waste soil, a large amount of demolished materials of buildings can be produced in urban construction, and part of demolished materials can be recycled to produce recycled aggregate, but in the process of producing the recycled aggregate, byproduct recycled micro powder accounting for about 10% -20% of the weight is produced, and the recycled micro powder is similar to the engineering waste soil in recycling at present and is mostly used as a filling material.
Currently, engineering waste is used as a filler, and the existing technology of calcining engineering waste and using the engineering waste as a cement mixed material is adopted, but the adopted calcining technology is long in time and high in energy consumption. Similarly, there are applications of the regenerated fine powder as a filler, as well as a simple carbon-fixing material, a cement admixture, or a concrete admixture by mineralizing the regenerated fine powder with carbon dioxide. The currently disclosed carbon dioxide mineralized and regenerated micro powder mostly adopts dry mineralization or wet mineralization, but the mineralization reaction process not only involves the diffusion of gas on the surface of powder, but also involves the reaction of gas and powder through medium water, so that the efficiency of dry mineralization is lower, and the energy consumption required by wet mineralization in the stirring process is higher. Although the pozzolanic activity of mineralized regenerated micropowder is higher than that of limestone, if only mineralized regenerated micropowder is used as cement admixture, the performance is still lower than that of cement admixture prepared by granulating blast furnace slag powder or fly ash which is commonly used at present.
Disclosure of Invention
Aiming at the technical problems, the invention provides the auxiliary cementing material, and the preparation method and application thereof, wherein the auxiliary cementing material has good compressive strength, can replace part of cement, and has low energy consumption, short time and high efficiency.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides an auxiliary cementing material which comprises flash clay and mineralized regenerated micro powder;
the preparation method of the flash clay specifically comprises the following steps: pulping and press-filtering engineering waste soil to obtain mud cakes, sequentially carrying out wet filtration, centrifugation, drying and grinding on the mud cakes to obtain clay powder, calcining the clay powder in a suspension state in air to obtain flash-burned clay, wherein the calcining temperature is 850-950 ℃, and the calcining time is 0.5-1.5 s;
the preparation method of the mineralized and regenerated micro powder specifically comprises the following steps: mineralizing the regenerated micro powder by a semi-dry method, drying and grinding to obtain mineralized regenerated micro powder, wherein the specific semi-dry mineralization steps comprise: spraying sodium hydroxide solution on the surface of the spread regenerated micro powder for wetting, and then mineralizing in an environment with the relative humidity of 80-100% RH.
The mud cake used for preparing the flash-burned clay consists of clay and quartz sand, and the particle size of clay minerals is generally smaller than that of quartz sand, so that the quartz sand can be removed as much as possible by adopting wet filtration, and the clay minerals are filtered into filtrate as much as possible, so that the specific gravity of the clay minerals in fine particle sediment obtained after the filtrate is centrifuged is improved. The clay powder contains minerals such as kaolinite, illite, montmorillonite, quartz and the like, and the main active ingredient is the kaolinite, and the kaolinite can be dehydroxylated by high-temperature calcination to form metakaolin with an amorphous structure. In addition, in the preparation method of the flash-burned clay, the clay powder is calcined in the air in a suspension state, so that the specific surface area of the clay powder is increased, the calcination efficiency is improved, the calcination time is obviously shortened compared with the prior art, and compared with the calcination mode in the prior art, the preparation efficiency is improved, and the energy is saved.
The regenerated micro powder used for preparing the mineralized regenerated micro powder is a byproduct in the process of producing the regenerated aggregate by using a demolition material, and mainly comprises hardened cement paste, wherein the main components of the cement paste comprise a small amount of unhydrated cement particles, calcium hydroxide, hydrated calcium aluminosilicate gel, ettringite, mono-sulfur hydrated calcium aluminate and the like. During the mineralization of carbon dioxide, the calcite is converted into calcium carbonate, and other components are decalcified to form aluminosilicate gel, and the aluminosilicate gel has pozzolanic activity; calcium carbonate not only participates in hydration reaction, but also provides nucleation sites to play a role in accelerating cement hydration reaction. The preparation method of mineralized regenerated micro powder provided by the invention adopts a semi-dry method to mineralize, and the dissolution of carbon dioxide in a liquid phase is accelerated due to the existence of a liquid-phase sodium hydroxide solution, so that the efficiency is higher compared with that of dry mineralization; moreover, because the sodium hydroxide solution adopts a spraying mode, the liquid amount on the surface of the regenerated micro powder is smaller than that of wet mineralization, carbon dioxide is easier to diffuse among the surfaces of the regenerated micro powder, continuous stirring operation in the wet mineralization process is not needed, and the required energy consumption is lower.
In combination with the first aspect, the particle size of the particles in the mud cake is less than 2.36mm, and the particles below the particle size can enable the particles forming the mud cake to be rapidly dispersed.
With reference to the first aspect, the specific steps of wet filtering, centrifuging, drying and grinding are as follows: mixing the mud cake with water according to the following ratio of 1: after being uniformly mixed in a mass ratio of 20-50, filtering and collecting filtrate by using a screen with a pore diameter not more than 25 mu m, centrifuging the obtained filtrate and collecting lower-layer fine particulate matter sediment; and (3) air-drying the fine particle precipitate until the water content is less than 5%, grinding and sieving to obtain clay powder, wherein the sieving pore diameter is 75 mu m.
With reference to the first aspect, the specific steps of semi-dry mineralization include: spreading the regenerated micro powder according to the standard with the thickness not more than 1mm after spreading, uniformly spraying sodium hydroxide solution on the surface of the spread regenerated micro powder according to the solid-liquid mass ratio of 0.01-0.1 to moisten the surface, and then mineralizing the moistened regenerated micro powder in an environment with the carbon dioxide concentration of 10-30 percent and the temperature of 20-30 ℃ and the relative humidity of 80-90 percent RH for mineralizing for not less than 1h.
Preferably, the mineralization temperature is 20-25 ℃, the mineralization time is 1-3 h, and the mineralization time can ensure the full progress of mineralization reaction.
With reference to the first aspect, the concentration of the sodium hydroxide solution is 3g/L to 5g/L.
In combination with the first aspect, the mass ratio of the flash clay to the mineralized regenerated micro powder is 1.5-2.2: 1, preferably 2:1, the mass ratio of the flash clay and the mineralized regenerated micro powder in the auxiliary cementing material can be adjusted to meet different requirements of the auxiliary cementing material on performances in different applications.
According to a second aspect of the invention, a preparation method of an auxiliary cementing material is provided, wherein the preparation method of the flash clay and the preparation method of mineralized regenerated micro powder are respectively used for preparing the flash clay and the mineralized regenerated micro powder, and the obtained flash clay and mineralized regenerated micro powder are prepared according to the following ratio of 1.5-2.2: mixing the materials according to the mass ratio of 1.
The preparation method comprises the steps of preparing the flash clay and preparing mineralized regenerated micro powder, wherein the preparation method of the flash clay effectively improves the calcination efficiency and forms metakaolin with an amorphous structure through controlling the calcination temperature and the calcination time; the preparation method of mineralized and regenerated micro powder does not need long-time stirring, and has simple operation and lower energy consumption.
The third aspect of the invention provides an application of the auxiliary cementing material in cementing material, wherein the auxiliary cementing material is used for preparing the cementing material, and the compressive strength of the obtained cementing material is equivalent to that of ordinary Portland cement.
With reference to the third aspect, the cementitious material further includes cement.
In combination with the third aspect, the cement in the cementing material accounts for 45-60% by mass.
In the cementing material containing the auxiliary cementing material and cement, the main active component of the flash clay in the auxiliary cementing material is metakaolin with an amorphous structure, and can dissolve out hydrated aluminate ions and hydrated silicate ions under alkaline conditions, and react with calcium ions dissolved out from the cement to generate hydrated calcium aluminosilicate gel; the main active ingredient in the mineralized regenerated micro powder in the auxiliary cementing material is nano calcium carbonate, and the calcium aluminosilicate gel formed by decalcification of hydrated calcium aluminosilicate reacts with calcium ions in cement to generate hydrated calcium aluminosilicate gel again; the carbonate ion dissolved out by nano calcium carbonate can react with calcium ion in cement, and hydrated aluminate ion dissolved out by cement or metakaolin to generate semi-carbon and monocarbon calcium aluminate hydrate. Therefore, the main active components of the flash clay and the mineralized regenerated micro powder contained in the auxiliary cementing material have a certain synergistic effect in the cement hydration reaction.
The invention has the beneficial effects that: the preparation method of the auxiliary cementing material provided by the invention has the advantages of short time, low energy consumption and high efficiency, the preparation of the flash clay and the mineralized regenerated micro powder can be completed under the conditions of short time and low energy consumption, and when the obtained auxiliary cementing material is applied to the cementing material, the performance of the composite cement obtained by mixing the auxiliary cementing material and the ordinary cement is equivalent to that of the ordinary silicate cement, so that the auxiliary cementing material can replace the ordinary silicate cement in a large proportion; and the performance fluctuation of the composite cement caused by complex engineering waste and construction materials can be stabilized by adjusting the proportion of the flash clay and the mineralized regenerated micro powder in the auxiliary cementing material.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The engineering spoil used in the embodiment and the comparative example is obtained from a certain building site in the southern mountain area of Shenzhen, and is dehydrated, pulped and press-filtered into mud cakes, and the mud cakes are press-filtered by a screen with the aperture of 2mm, and are air-dried, wherein the chemical composition of the air-dried mud cakes is as follows by weight of oxide:
| chemical composition | Mass ratio (%) |
| Silica dioxide | 61.2 |
| Alumina oxide | 20.7 |
| Iron oxide | 5.2 |
| Potassium oxide | 3.2 |
| Loss on ignition | 9.7 |
。
The regenerated micro powder used in the examples and the comparative examples of the invention is obtained by sieving regenerated fine aggregate with the grain diameter of less than 2.36mm by a 75 μm sieve in the process of producing the regenerated aggregate by using the demolition materials, and the chemical composition of the regenerated micro powder is as follows by weight of oxide:
| chemical composition | Mass ratio (%) |
| Calcium oxide | 32.1 |
| Silica dioxide | 35.8 |
| Alumina oxide | 3.2 |
| Magnesium oxide | 9.4 |
| Sulfur trioxide | 2.1 |
| Others | 1.9 |
| Loss on ignition | 15.5 |
。
The cement used in the examples and comparative examples of the present invention is pure Portland cement, which is prepared by grinding cement clinker of class P.I 42.5R with dihydrate gypsum, and the chemical composition of the cement is as follows by weight of oxide:
| chemical composition | Mass ratio (%) |
| Calcium oxide | 67.0 |
| Silica dioxide | 18.6 |
| Alumina oxide | 5.4 |
| Magnesium oxide | 1.3 |
| Sulfur trioxide | 3.1 |
| Iron oxide | 3.0 |
| Others | 1.6 |
。
The sodium hydroxide used in the examples and the comparative examples is analytically pure, and the purity is more than or equal to 96%; the carbon dioxide gas is high-purity gas with purity of 99.99%; the compressed air is high-purity air with the purity of 99.999%; the water reducer is polycarboxylate water reducer.
Example 1
The embodiment provides a preparation method of auxiliary cementing material flash clay, which comprises the following specific steps:
(1) Uniformly mixing the air-dried mud cake with water in a mass ratio of 1:35 to prepare mud with fully dispersed particulate matters;
(2) Filtering the slurry through a screen with the aperture of 25 mu m to obtain filtrate;
(3) Centrifuging the filtrate in a centrifuge at a gravitational acceleration of 1000g for 10 minutes, and discharging supernatant to obtain fine particulate precipitate;
(4) Air-drying the fine particulate matter precipitate under natural condition until the water content is less than 5%, grinding and passing through 75 μm sieve to obtain clay powder;
(5) Mixing clay powder with compressed air, spraying from the top of the vertical tube furnace, dispersing clay powder in suspension state, setting the temperature in the furnace to 900 ℃, and calcining for 1.0s to obtain the flash clay.
Example 2
The embodiment provides a preparation method of auxiliary cementing material flash clay, which comprises the following specific steps:
(1) Uniformly mixing the air-dried mud cake with water in a mass ratio of 1:20 to prepare mud with fully dispersed particulate matters;
(2) Filtering the slurry through a screen with the aperture of 25 mu m to obtain filtrate;
(3) Centrifuging the filtrate in a centrifuge at a gravitational acceleration of 1000g for 15 minutes, and discharging supernatant to obtain fine particulate precipitate;
(4) Air-drying the fine particulate matter precipitate under natural condition until the water content is less than 5%, grinding and passing through 75 μm sieve to obtain clay powder;
(5) Mixing clay powder with compressed air, spraying from the top of the vertical tube furnace, dispersing clay powder in suspension state, setting the temperature in the furnace to 850 ℃, and calcining for 0.5s to obtain the flash clay.
Example 3
The embodiment provides a preparation method of auxiliary cementing material flash clay, which comprises the following specific steps:
(1) Uniformly mixing the air-dried mud cake with water in a mass ratio of 1:50 to prepare mud with fully dispersed particulate matters;
(2) Filtering the slurry through a screen with the aperture of 25 mu m to obtain filtrate;
(3) Centrifuging the filtrate in a centrifuge at a gravitational acceleration of 1000g for 10 minutes, and discharging supernatant to obtain fine particulate precipitate;
(4) Air-drying the fine particulate matter precipitate under natural condition until the water content is less than 5%, grinding and passing through 75 μm sieve to obtain clay powder;
(5) Mixing clay powder with compressed air, spraying from the top of the vertical tube furnace, dispersing clay powder in suspension state, setting the temperature in the furnace at 950 ℃, and calcining for 1.5s to obtain the flash clay.
Example 4
The embodiment provides a preparation method of auxiliary cementing material mineralized regenerated micro powder, which comprises the following specific steps:
(1) Flattening the regenerated micro powder obtained by sieving with a 75 μm sieve in a stainless steel tray, wherein the thickness of the powder is 1mm;
(2) 4g/L sodium hydroxide aqueous solution is mixed according to the solid-liquid mass ratio of 0.05:1 are uniformly sprayed on the surface of the spread regenerated micro powder in proportion to moisten the surface;
(3) Placing the wetted regenerated micro powder in an environment with carbon dioxide concentration of 20%, temperature of 25 ℃ and relative humidity of 90% RH for reaction for 2 hours;
(4) And (3) air-drying the regenerated micro powder after the reaction under natural conditions until the water content is less than 5%, grinding and passing through a 75-mu m screen to obtain mineralized regenerated micro powder.
Example 5
The embodiment provides a preparation method of auxiliary cementing material mineralized regenerated micro powder, which comprises the following specific steps:
(1) Flattening the regenerated micro powder obtained by sieving with a 75 μm sieve in a stainless steel tray, wherein the thickness of the powder is 0.8mm;
(2) 3g/L sodium hydroxide aqueous solution is mixed according to the solid-liquid mass ratio of 0.01:1 are uniformly sprayed on the surface of the spread regenerated micro powder in proportion to moisten the surface;
(3) Placing the wetted regenerated micro powder into an environment with carbon dioxide concentration of 10%, temperature of 20 ℃ and relative humidity of 80% RH for reaction for 1 hour;
(4) And (3) air-drying the regenerated micro powder after the reaction under natural conditions until the water content is less than 5%, grinding and passing through a 75-mu m screen to obtain mineralized regenerated micro powder.
Example 6
The embodiment provides a preparation method of auxiliary cementing material mineralized regenerated micro powder, which comprises the following specific steps:
(1) Flattening the regenerated micro powder obtained by sieving with a 75 μm sieve in a stainless steel tray, wherein the thickness of the powder is 1.0mm;
(2) 5g/L sodium hydroxide aqueous solution is mixed according to the solid-liquid mass ratio of 0.1:1 are uniformly sprayed on the surface of the spread regenerated micro powder in proportion to moisten the surface;
(3) Placing the wetted regenerated micro powder in an environment with carbon dioxide concentration of 30%, temperature of 30 ℃ and relative humidity of 100% RH for reaction for 3 hours;
(4) And (3) air-drying the regenerated micro powder after the reaction under natural conditions until the water content is less than 5%, grinding and passing through a 75-mu m screen to obtain mineralized regenerated micro powder.
Example 7
This example provides a supplementary cementitious material composed of the flash clay prepared in example 1 and the mineralized regenerated micro powder prepared in example 4, and its application in the cementitious material, and the composition ratios of the supplementary cementitious material and the cementitious material are shown in table 1.
Example 8
This example provides a supplementary cementitious material composed of the flash clay prepared in example 2 and the mineralized regenerated micro powder prepared in example 5, and its application in the cementitious material, and the composition ratios of the supplementary cementitious material and the cementitious material are shown in table 1.
Example 9
This example provides a supplementary cementitious material composed of the flash clay prepared in example 3 and the mineralized regenerated micro powder prepared in example 6, and its application in the cementitious material, and the composition ratios of the supplementary cementitious material and the cementitious material are shown in table 1.
Examples 10 to 12
This example provides a supplementary cementitious material composed of the flash clay prepared in example 1 and the mineralized regenerated micro powder prepared in example 4, and its application in the cementitious material, and the composition ratios of the supplementary cementitious material and the cementitious material are shown in table 1.
Comparative example 1
This comparative example provides a process for preparing a flash clay, the specific steps being similar to example 1, except that the clay powder is calcined at 800 ℃ for 2 hours under calcination conditions.
Comparative example 2
The comparative example provides a preparation method of dry mineralized regenerated micro powder, which comprises the following specific steps: spreading the regenerated micropowder in a stainless steel tray, wherein the thickness of the powder is 1.0mm, and placing the powder in an environment with the carbon dioxide concentration of 20 percent and the relative humidity of 60 percent RH for reacting for 2 hours at the temperature of 25 ℃ to obtain the dry mineralized regenerated micropowder.
Comparative example 3
The comparative example provides a method for preparing semi-dry mineralized regenerated micro powder, which has the specific steps similar to those of example 4, except that sodium hydroxide solution is replaced by pure water for spraying, so as to obtain the semi-dry mineralized regenerated micro powder (water spraying).
Comparative examples 4 to 7
Comparative examples 4 to 7 provide 4 kinds of cement materials, wherein the calcined clay used in comparative example 5 was prepared in comparative example 1, the calcined clay and the dry mineralized regenerated micropowder used in comparative example 6 were prepared in comparative example 1 and comparative example 2, respectively, and the semi-dry mineralized regenerated micropowder (water spray) and the flash clay used in comparative example 7 were prepared in comparative example 3 and example 2, respectively. The composition ratios of the cementing materials in comparative examples 4 to 7 are shown in Table 1.
Table 1 the composition ratios of the gelling materials in examples 7 to 12 and comparative examples 4 to 7
Test example 1
The results of X-ray diffraction analysis of the calcined clay obtained in examples 1 to 3 and the calcined clay obtained in comparative example 1, respectively, were shown in Table 2, with 20% zinc oxide powder incorporated therein.
Table 2X-ray diffraction results of examples 1 to 3 and comparative example 1
| Examples | Amorphous content (%) |
| Example 1 | 26.9 |
| Example 2 | 21.8 |
| Example 3 | 33.2 |
| Comparative example 1 | 39.6 |
。
As can be seen from the test results in Table 2, the flash firing method used in examples 1 to 3 has a great advantage over the conventional calcination in terms of the efficiency and energy consumption, although the calcination time is short and the complete conversion of the kaolinite into metakaolin is not yet possible. The greatly increased amorphous content of example 3 compared to example 2 shows that higher temperatures and longer calcination times favor the conversion of kaolinite to metakaolin over a range of temperatures and times.
Test example 2
The mineralized regenerated fine powder obtained in examples 4 to 6, the dry mineralized regenerated fine powder obtained in comparative example 2 and the semi-dry mineralized regenerated fine powder (water spray) obtained in comparative example 3 were subjected to thermal weight loss analysis, respectively, and the results are shown in Table 3.
Table 3 results of thermal weight loss for examples 4 to 6 and comparative examples 2 to 3
As is clear from the test results in Table 3, the mineralization efficiency of the semi-dry mineralization in examples 4 to 6 is greatly improved compared with that of the dry mineralization in comparative example 2, and the semi-dry mineralization efficiency of the regenerated micro powder wetted by pure water is also improved compared with that of comparative example 3, which indicates that the carbon dioxide solidified by the semi-dry mineralization of the regenerated micro powder by spraying a sodium hydroxide solution with a certain concentration is more.
The increased calcium carbonate content of example 6 compared to example 5 shows that a higher humidity and longer mineralization time favors the phase conversion of set cement to calcium carbonate over a range of humidity and mineralization time.
Test example 3
The cement paste was prepared by mixing the cement materials provided in examples 7 to 12 and comparative examples 4 to 7 with water in a mass ratio of 0.35, and adding a water reducing agent in an amount of 0.5% by weight of the cement material, and the mechanical strength of the resulting cement paste was tested, respectively, and the results are shown in table 4.
TABLE 4 mechanical Properties of Cement paste corresponding to gel materials of examples 7 to 12 and comparative examples 4 to 7
As can be seen from the data in table 4, in examples 7 to 9, the mechanical properties of the paste were slightly improved with the improvement of the active ingredients in the supplementary cementitious material. Nevertheless, the particle-filling effect of the supplementary cementitious material still contributes significantly to the strength. Although the reduction in the proportion of cement in the cement in examples 10 and 12 resulted in a reduction in the net slurry strength, the amount of cement used was reduced and the resulting net slurry strength still met the use requirements as compared to example 7; the decrease in the proportion of the flash clay in the supplementary cementitious material of example 11 decreased the early strength of the neat paste, indicating that the relationship of the proportion of flash clay to mineralized regenerated fines has an effect on its synergy.
In addition, the mechanical properties of the pure Portland cement paste in the other examples and comparative example 4 are not significantly different or slightly improved except example 10, which indicates that the composite cement prepared from the auxiliary cementing material is equivalent to the pure Portland cement in performance; compared with the limestone calcined clay cement of comparative example 5, although the strength is not significantly different, the mineralized regenerated micropowder replaces natural raw materials, and the preparation process solidifies carbon dioxide, so that the method has the advantage of reducing the carbon footprint of the cementing material; compared with comparative example 5, the active ingredients in the dry mineralized regenerated micro powder are lower, the synergistic effect with calcined clay is weaker, and the early strength of the clean slurry is greatly influenced; the supplementary cementitious material of comparative example 7 contained semi-dry mineralized regenerated micro powder (water spray), and the early strength of the slurry was reduced compared to example 8 due to the relatively low content of active ingredients.
According to the analysis, the mechanical property of the cementing material prepared by compounding the auxiliary cementing material provided by the invention with cement is equivalent to that of the cementing material prepared by using pure silicate cement, so that the auxiliary cementing material provided by the invention can replace ordinary silicate cement in a large proportion.
The foregoing description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. An auxiliary cementing material is characterized by comprising flash clay and mineralized regenerated micro powder;
the preparation method of the flash clay specifically comprises the following steps: pulping and press-filtering engineering waste soil to obtain mud cakes, sequentially carrying out wet filtration, centrifugation, drying and grinding on the mud cakes to obtain clay powder, and calcining the clay powder in a suspension state in air to obtain flash-burned clay, wherein the calcining temperature is 850-950 ℃ and the calcining time is 0.5-1.5 s;
the preparation method of the mineralized and regenerated micro powder specifically comprises the following steps: mineralizing the regenerated micro powder by a semi-dry method, drying and grinding to obtain mineralized regenerated micro powder, wherein the specific semi-dry mineralization steps comprise: spraying sodium hydroxide solution on the surface of the spread regenerated micro powder for wetting, and then mineralizing in an environment with the relative humidity of 80-100% RH.
2. The supplementary cementitious material of claim 1, wherein the particles in the mudcake have a particle size of less than 2.36mm.
3. The supplementary cementitious material according to claim 1 or 2, wherein the specific steps of wet filtration, drying and grinding are: mixing the mud cake with water according to the following ratio of 1: after being uniformly mixed in a mass ratio of 20-50, filtering and collecting filtrate by using a screen with a pore diameter not more than 25 mu m, centrifuging the obtained filtrate and collecting lower-layer fine particulate matter sediment; and (3) air-drying the fine particle precipitate until the water content is less than 5%, and grinding and sieving to obtain clay powder.
4. The supplementary cementitious material as set forth in claim 1, wherein the specific step of semi-dry mineralization includes: spreading the regenerated micro powder according to the standard with the thickness not more than 1mm after spreading, uniformly spraying sodium hydroxide solution on the surface of the spread regenerated micro powder according to the solid-liquid mass ratio of 0.01-0.1 to moisten the surface, and then mineralizing the moistened regenerated micro powder in an environment with the carbon dioxide concentration of 10-30 percent and the temperature of 20-30 ℃ and the relative humidity of 80-90 percent RH for mineralizing for not less than 1h.
5. The supplementary cementitious material of claim 1 or 4, wherein the concentration of the sodium hydroxide solution is 3g/L to 5g/L.
6. The auxiliary cementing material according to claim 1, wherein the mass ratio of the flash clay to the mineralized regenerated micro powder is 1.5-2.2: 1.
7. a method for preparing a supplementary cementitious material, characterized in that the method for preparing the flash clay and the mineralized regenerated micro powder in the supplementary cementitious material according to any one of claims 1 to 6 respectively prepares the flash clay and the mineralized regenerated micro powder according to 1.5 to 2.2: mixing the materials according to the mass ratio of 1.
8. Use of a supplementary cementitious material according to any one of claims 1 to 6 or a supplementary cementitious material prepared according to the method of preparation of claim 7 in a cementitious material.
9. The use of claim 8, wherein the cementitious material further comprises cement.
10. The use according to claim 9, wherein the cement content of the cement is 45-60% by mass.
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