CN108675657B - Method for preparing silicate-sulphoaluminate composite system clinker by using waste residues - Google Patents
Method for preparing silicate-sulphoaluminate composite system clinker by using waste residues Download PDFInfo
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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
- C04B7/02—Portland cement
- C04B7/04—Portland cement using raw materials containing gypsum, i.e. processes of the Mueller-Kuehne type
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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
- C04B7/32—Aluminous cements
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
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- 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 disclosesA method for preparing silicate-sulphoaluminate composite system clinker by using waste residues comprises the steps of grinding and homogenizing carbide slag, industrial waste residues phosphogypsum, pyrite residues, sandstone and bauxite, and calcining at 1280-1400 ℃ to prepare the silicate-sulphoaluminate composite system clinker. Wherein the clinker is mainly composed of the following minerals by weight percent: 49 to 64 percent of C3S and
34 to 50 percent of C2S、C3A and C4An AF mineral. The invention provides an early strength and high strength composite cement clinker with continuously developed strength for engineering construction under the conditions of rapid first-aid repair, low temperature, corrosion resistance and the like. Meanwhile, industrial wastes can be efficiently and reasonably utilized, waste residue pollution is reduced, the cement production cost is reduced, and the economic benefit and the social benefit of a cement enterprise are improved.
Description
Technical Field
The invention relates to the technical field of cement material preparation, in particular to a method for preparing silicate-sulphoaluminate composite system clinker by using waste residues, which is suitable for engineering construction application requiring early strength and high strength.
Background
Cement and cement-based composites are the largest man-made materials used in the world. Since the invention of the silicate system cement, the clinker mineral composition is stable, the technical equipment is mature, and the relatively stable large-scale and integrated production is realized. But currently used in large quantitiesThe acid salt cement has some disadvantages and shortcomings, which are mainly shown as follows: the early strength is low, about 20-28 MP; the firing temperature is high, namely 1450 ℃, so that the energy consumption is high; alite (C) in cement clinker3S) content is high, usually about 55 percent (mass fraction), sometimes even as high as 60 percent, the requirement on the quality of limestone raw materials is high, and a large amount of high-quality limestone resources are consumed. Due to the large amount of limestone, a large amount of CO is produced2And the environmental pollution is becoming serious.
The sulphoaluminate cement is a new cement variety after portland cement and aluminate cement, and has the advantages of high early strength, high strength, frost resistance, impermeability, corrosion resistance and the like. At present, the price of the sulphoaluminate cement is about 1000 yuan per ton, and the price of the high-grade bauxite is about 1500 yuan per ton as one of the raw materials required by the sulphoaluminate cement. The use of high-grade aluminum raw materials becomes one of the main costs of sulphoaluminate cement production, and to a certain extent, the high cost of raw materials limits the production and market application of sulphoaluminate cement.
A large amount of various industrial waste residues are discharged every year in China, and if the industrial waste residues are treated in a landfill mode, a large amount of land is occupied, and secondary pollution to air and water sources is caused due to alkalization of the land. The components and properties of the industrial waste residues are close to those of some natural minerals, if the useful minerals with potential performance can be utilized, the environmental pollution caused by the waste residues and the waste gases is reduced and treated, the industrial waste residues are recycled, products with high added values are synthesized, and the method has outstanding social and economic benefits.
The Portland cement has the characteristics of stable performance and low production cost, but the early strength is slowly developed, and the sulphoaluminate cement has the characteristics of early strength, high strength, low alkali and the like, but the production cost is higher. Both series of cements have their own unique mineral composition and performance characteristics, while both have inevitable disadvantages. If the excellent properties can be combined by compounding, the product C is produced by certain processing technology and technical measures3S、C2S and
the main research subject of the present invention is cement clinker which is a main mineral. And if the existing natural ores, industrial tailings and the like can be utilized as raw materials as far as possible, the method is favorable for reducing the firing temperature, expanding the variety types and the application range of cement, reducing the use amount of calcium carbonate and achieving the purposes of saving energy and reducing the emission of carbon dioxide.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for preparing silicate-sulphoaluminate composite system clinker by using waste residues, the cement clinker has the characteristics of early strength and high strength for continuous development of strength, and the method not only can reduce and treat environmental pollution caused by the waste residues, but also can recycle the waste residues and synthesize products with high added values.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing silicate-sulphoaluminate composite system clinker by using waste residues comprises the following steps:
(1) preparation of composite cement raw material: the weight percentages are as follows: mixing 50-70% of dry carbide slag, 5-10% of dry waste residue phosphogypsum, 3-5% of dry sulfate slag, 2-5% of sandstone and 20-30% of bauxite uniformly, and grinding to obtain a composite cement raw material; wherein the water content of the carbide slag, the waste residue phosphogypsum, the sulfate slag and the bauxite is less than 0.5 wt%;
(2) preparing the composite cement clinker: calcining the composite cement raw material prepared in the step (1) at 1280-1400 ℃ for 30-40 minutes, cooling the material after calcination, and crushing and grinding the material to obtain silicate-sulphoaluminate composite system clinker; wherein the mineral composition in the clinker is 49-64% of C3S and
34 to 50 percent of C2S、C3A and C4AF mineral, 1-4% of vitreous, wherein C2S is 2CaO ∙ SiO2，C3A is 3CaO ∙ Al2O3，C4AF is 4CaO ∙ Al2O3∙Fe2O3，C3S is 3CaO ∙ SiO2，
Is 3CaO ∙ 3Al2O3∙CaSO4。
Preferably, the alkalinity coefficient is controlled to be 0.92-1.28, the aluminum-sulfur ratio is controlled to be 3.18-5.10, the aluminum-silicon ratio is 0.80-0.90, the lime saturation coefficient is 0.35-0.65, and the silicic acid rate is 0.70-0.90 when the raw material is compounded in the step (1); the values are expressed as:
alkalinity coefficient:
aluminum-sulfur ratio:
the ratio of aluminum to silicon:
lime saturation coefficient:
silicic acid ratio:
preferably, in the step (1), the components are respectively ground into powder, and the fineness of the powder is 10-16% of the screen residue with the particle size of 80 mu m.
In specific practice, the calcination in step (2) may be carried out in a high temperature calciner, rotary kiln, shaft kiln or tunnel kiln.
Preferably, the material in the step (2) is cooled to a temperature 0-60 ℃ higher than the room temperature within 20-30 minutes.
In specific implementation, the clinker fired in the step (2) can be cooled by an electric fan or a grate cooler.
The technical principle is as follows: the silicate cement is prepared from calcareous, clayey, iron and siliceous raw materialsIs a raw material component. For silicate system minerals, C appears in the material in large amount at 1300 deg.C or above3A and C4Liquid phase of mainly AF, etc., C2The S content reaches the maximum value; the presence of a liquid phase causes C to be formed as the temperature increases2S and CaO are gradually fused in liquid phase to react to generate C3S, thereby forming the various mineral components of the silicate system. The sulphoaluminate cement is prepared by using limestone, bauxite and gypsum as main raw materials and through reaction at low temperature of about 1350 deg.c
And C2Clinker with S as main component and small amount of C in mineral4AF，
And C of silicate system3S is the same, mainly achieving early strength of the cement. By synthesizing the factors of raw material type, firing temperature, raw material fineness and the like, and controlling the alkalinity coefficient, the aluminum-sulfur ratio, the aluminum-silicon ratio, the lime saturation coefficient and the silicic acid ratio, the formation of clinker minerals is controlled, so that C in the silicate-sulphoaluminate composite system clinker is realized3S and
49% -64% of minerals and C2S、C3A and C4The AF mineral is in a clinker system of 34-50%.
Has the advantages that: the silicate-sulphoaluminate composite system clinker prepared by the invention utilizes C3S and
primarily early strength provided, C2The S mainly provides the later strength, thereby realizing various physical and chemical properties required by the silicate-sulphoaluminate composite system clinker, having the characteristics of continuous development of the later strength of the silicate cement, and having the characteristics of quick setting and hardening, high strength, micro-expansibility, corrosion resistance and the like of the sulphoaluminate cement, and being an early-strength and high-strength type clinker with continuous development of strengthA novel composite cement clinker. The method for preparing the silicate-sulphoaluminate composite system clinker by using the waste residues utilizes industrial solid wastes such as carbide slag, industrial waste residues such as phosphogypsum and pyrite cinder, and the like to prepare the novel cement clinker, opens up an effective way for saving energy, utilizing waste, reducing cost and improving cement performance, and embodies the aim of changing waste into valuable and developing circular economy. The method not only reduces and treats the environmental pollution caused by the waste residue, but also recycles the waste residue, synthesizes products with high added value, and has outstanding social and economic benefits.
Drawings
FIG. 1 is a flow chart of the production process of the present invention.
Detailed Description
The invention provides a method for preparing silicate-sulphoaluminate composite system clinker by using waste residues. The method comprises the following steps of firstly, respectively drying the carbide slag, the waste residue phosphogypsum, the sulfuric acid slag and the bauxite until the water content of the carbide slag, the waste residue phosphogypsum, the sulfuric acid slag and the bauxite is less than 0.5 wt%, wherein the specific formula comprises the following components in percentage by weight: 50-70% of dry carbide slag, 5-10% of dry waste residue phosphogypsum, 3-5% of dry sulfate slag, 2-5% of sandstone and 20-30% of bauxite; the alkalinity coefficient is 0.92-1.28, the aluminum-sulfur ratio is 3.18-5.10, the aluminum-silicon ratio is 0.80-0.90, the lime saturation coefficient is 0.35-0.65, and the silicic acid rate is 0.70-0.90. Grinding the components respectively to obtain 10-16% of screen residue with fineness of 80 μm, mixing the components uniformly, and homogenizing to obtain a composite cement raw material; calcining the prepared composite cement raw material at 1280-1400 ℃ for 30-40 minutes, wherein the calcination can be carried out in a high-temperature calciner, a rotary kiln, a vertical kiln or a tunnel kiln. And cooling the material after calcining and sintering, wherein the material is cooled to a temperature 0-60 ℃ higher than the room temperature in 20-30 minutes, and the sintered clinker is cooled by using an electric fan or a grate cooler. Grinding or crushing to obtain the silicate-sulphoaluminate composite system clinker. Wherein the mineral composition in the clinker is 49-64% of C3S and
34 to 50 percent of C2S、C3A and C4An AF mineral.
The present invention will be described in further detail with reference to specific examples.
The chemical compositions of various industrial waste residues and industrial waste residues used in examples 1 to 3 are shown in Table 1:
| material(s) | L.O.I | SiO2 | Al2O3 | TiO2 | Fe2O3 | CaO | MgO | K2O | Na2O | SO3 | Cl￣ |
| Carbide slag | 26.01 | 3.72 | 1.18 | 0.05 | 0.33 | 67.97 | 0.05 | 0.02 | 0.11 | 0.21 | 0.030 |
| Bauxite | 1.31 | 39.89 | 52.83 | 0.86 | 2.65 | 0.87 | 0.24 | 0.25 | 0.11 | 0.06 | 0.005 |
| Phosphogypsum | 20.78 | 0.26 | 0.08 | 0.00 | 0.06 | 32.83 | 0.00 | 0.00 | 0.01 | 46.00 | 0.002 |
| Sandstone | 2.03 | 80.17 | 8.98 | 0.56 | 4.53 | 0.63 | 0.30 | 1.75 | 0.09 | 0.06 | 0.003 |
| Sulfuric acid slag | 7.23 | 31.47 | 6.88 | 1.08 | 31.56 | 9.98 | 5.96 | 0.58 | 0.83 | 3.14 | 0.006 |
Example 1
The three types of carbide slag, waste residue phosphogypsum and pyrite cinder are dried at 105 ℃ until the moisture of the carbide slag, the waste residue phosphogypsum and the pyrite cinder is less than 0.5 wt%, and the weight percentages of the specific formula components are as follows: 70.0 percent of carbide slag, 20.0 percent of bauxite, 5.0 percent of dry waste residue phosphogypsum, 2.0 percent of sandstone and 3.0 percent of dry pyrite cinder. Wherein the alkalinity coefficient is 1.28, the aluminum-sulfur ratio is 3.18, the aluminum-silicon ratio is 0.80, the lime saturation coefficient is 0.65, and the silicic acid rate is 0.70. Grinding the above components respectively to obtain fineness of 80 μm and screen residue of about 14%, mixing, and homogenizing to obtain composite cement raw material(ii) a The prepared composite cement raw material is calcined for 35 minutes at 1340 +/-40 ℃, and the calcination is carried out in a vertical kiln. Grinding or crushing the material after calcining to obtain the silicate-sulphoaluminate composite system clinker. Wherein the mineral composition in the clinker is 61% of C3S and
36% of C2S、C3A and C4AF mineral, 3% vitreous, with a specific surface area of 4000cm2The initial setting time is 76min, the final setting time is 156min, the 3d compressive strength is 47.9MPa, the 7d compressive strength is 48.5MPa, the 28d compressive strength is 71.3MPa, and the stability (boiling method) is qualified, so that the clinker achieves the early-strength and high-strength effect of continuous development of strength.
Example 2
The three industrial waste residues of the carbide slag, the waste residue of the phosphogypsum and the pyrite cinder are dried at 105 ℃ until the moisture of the carbide slag, the waste residue of the phosphogypsum and the pyrite cinder is less than 0.5 wt%, and the weight percentages of the specific formula components are as follows: 65.0 percent of dry carbide slag, 21.0 percent of bauxite, 6.0 percent of dry waste residue phosphogypsum, 3.0 percent of sandstone and 5.0 percent of dry pyrite cinder. Wherein the alkalinity coefficient is 1.23, the aluminum-sulfur ratio is 3.86, the aluminum-silicon ratio is 0.82, the lime saturation coefficient is 0.61, and the silicic acid rate is 0.87. Grinding the components respectively to obtain fineness of about 12% of 80 μm screen residue, mixing the components uniformly, and homogenizing to obtain composite cement raw material; the prepared composite cement raw material is calcined for 40 minutes at 1350 +/-40 ℃, and the calcination is carried out in a high-temperature calcining furnace. Cooling the material after calcining and sintering, wherein the material needs to be cooled to room temperature within 30 minutes, and the calcined clinker is cooled by an electric fan. Grinding or crushing to obtain the silicate-sulphoaluminate composite system clinker. Wherein the mineral composition in the clinker is 59% of C3S and
mineral, 37% C2S、C3A and C4AF, 4% vitreous, specific surface area measured 3800cm2G, initial setting time of 68min, final setting time of 132min, 3d compressive strength of 43.6MPa, 7d resistanceThe compressive strength is 47.2MPa, the 28d compressive strength is 69.8MPa, and the stability (boiling method) is qualified, so that the clinker achieves the early-strength and high-strength effects of continuous development of strength.
Example 3
The three types of carbide slag, waste residue phosphogypsum and pyrite cinder are dried at 105 ℃ until the moisture of the carbide slag, the waste residue phosphogypsum and the pyrite cinder is less than 0.5 wt%, and the weight percentages of the specific formula components are as follows: 60.0 percent of carbide slag, 25.0 percent of bauxite, 9.0 percent of dry waste residue phosphogypsum, 2.0 percent of sandstone and 4.0 percent of dry pyrite cinder. Wherein the alkalinity coefficient is 1.06, the aluminum-sulfur ratio is 4.31, the aluminum-silicon ratio is 0.86, the lime saturation coefficient is 0.49, and the silicic acid rate is 0.83. Grinding the components respectively to obtain fineness of about 10% of 80 μm screen residue, mixing the components uniformly, and homogenizing to obtain composite cement raw material; the prepared composite cement raw material is calcined for 30 minutes at 1340 +/-40 ℃, and the calcination is carried out in a tunnel kiln. Grinding or crushing the material after calcining to obtain the silicate-sulphoaluminate composite system clinker. Wherein the mineral composition in the clinker is 64% of C3S and
34% of C2S、C3A and C4AF mineral, 2% vitreous, specific surface area 3600cm2The initial setting time is 71min, the final setting time is 169min, the 3d compressive strength is 48.3MPa, the 7d compressive strength is 49.5MPa, the 28d compressive strength is 73.1MPa, and the stability (boiling method) is qualified, so that the clinker achieves the early-strength and high-strength effect of continuous development of strength.
Example 4
The three industrial waste residues of the carbide slag, the waste residue of the phosphogypsum and the pyrite cinder are dried at 105 ℃ until the moisture of the carbide slag, the waste residue of the phosphogypsum and the pyrite cinder is less than 0.5 wt%, and the weight percentages of the specific formula components are as follows: 56.0 percent of dry carbide slag, 28.0 percent of bauxite, 8.0 percent of dry waste residue phosphogypsum, 3.4 percent of sandstone and 4.6 percent of dry pyrite cinder. Grinding the components respectively to obtain fineness of about 12% of 80 μm screen residue, mixing the components uniformly, and homogenizing to obtain composite cement raw material; wherein the alkalinity factor0.99, 5.01 of aluminum-sulfur ratio, 0.90 of aluminum-silicon ratio, 0.35 of lime saturation coefficient and 0.90 of silicic acid ratio. The prepared composite cement raw material is calcined for 30 minutes at 1360 +/-40 ℃, and the calcination is carried out in a rotary kiln. And cooling the material after the calcining and sintering, wherein the material is cooled to 60 ℃ in 25 minutes, and the calcined clinker is cooled by using a grate cooler. Grinding or crushing to obtain the silicate-sulphoaluminate composite system clinker. Wherein the mineral composition in the clinker is 53% of C3S and
46% of C2S、C3A and C4AF mineral, 1% vitreous, 3500cm specific surface area2The initial setting time is 83min, the final setting time is 142min, the 3d compressive strength is 42.6MPa, the 7d compressive strength is 45.3MPa, the 28d compressive strength is 68.3MPa, and the stability (boiling method) is qualified, so that the clinker achieves the early strength and high strength effect of continuous strength development.
Example 5
The three types of carbide slag, waste residue phosphogypsum and pyrite cinder are dried at 105 ℃ until the moisture of the carbide slag, the waste residue phosphogypsum and the pyrite cinder is less than 0.5 wt%, and the weight percentages of the specific formula components are as follows: 50.0 percent of carbide slag, 30.0 percent of bauxite, 10.0 percent of dry waste residue phosphogypsum, 5.0 percent of sandstone and 5.0 percent of dry pyrite cinder. Wherein the alkalinity coefficient is 0.92, the aluminum-sulfur ratio is 5.10, the aluminum-silicon ratio is 0.89, the lime saturation coefficient is 0.56, and the silicic acid rate is 0.88. Grinding the components respectively to obtain fineness of about 16% of 80 μm screen residue, mixing the components uniformly, and homogenizing to obtain composite cement raw material; the prepared composite cement raw material is calcined for 40 minutes at the temperature of 1320 +/-40 ℃, and the calcination is carried out in a vertical kiln. Grinding or crushing the material after calcining to obtain the silicate-sulphoaluminate composite system clinker. Wherein the mineral composition in the clinker is 49% of C3S and
50% of C2S、C3A and C4AF mineral, 1% vitreous, with a specific surface area of 3800cm2G, initial setting time79min, 173min of final setting time, 41.9MPa of 3d compressive strength, 43.5MPa of 7d compressive strength and 64.8MPa of 28d compressive strength, and qualified stability (boiling method), so that the clinker achieves the early strength and high strength effects of continuous development of strength.
Claims (5)
1. A method for preparing silicate-sulphoaluminate composite system clinker by using waste residues is characterized by comprising the following steps:
(1) preparation of composite cement raw material: the weight percentages are as follows: mixing 50-70% of dry carbide slag, 5-10% of dry waste residue phosphogypsum, 3-5% of dry sulfate slag, 2-5% of sandstone and 20-30% of bauxite uniformly, and grinding to obtain a composite cement raw material; wherein the water content of the carbide slag, the waste residue phosphogypsum, the sulfate slag and the bauxite is less than 0.5 wt%;
(2) preparing the composite cement clinker: calcining the composite cement raw material prepared in the step (1) at 1280-1400 ℃ for 30-40 minutes, cooling the material after calcination, and crushing and grinding the material to obtain silicate-sulphoaluminate composite system clinker; wherein the mineral composition in the clinker is 49-64% of C3S and
34 to 50 percent of C2S、C3A and C4AF mineral, 1-4% of vitreous, wherein C2S is 2CaO ∙ SiO2，C3A is 3CaO ∙ Al2O3，C4AF is 4CaO ∙ Al2O3∙Fe2O3，C3S is 3CaO ∙ SiO2，
Is 3CaO ∙ 3Al2O3∙CaSO4；
Controlling the alkalinity coefficient to be 0.92-1.28, the aluminum-sulfur ratio to be 3.18-5.10, the aluminum-silicon ratio to be 0.80-0.90, the lime saturation coefficient to be 0.35-0.65 and the silicic acid rate to be 0.70-0.90 during raw material proportioning in the step (1); the values are expressed as:
alkalinity coefficient:
aluminum-sulfur ratio:
the ratio of aluminum to silicon:
lime saturation coefficient:
silicic acid ratio:
2. the method for preparing the silicate-sulphoaluminate composite system clinker by using the waste residue as claimed in claim 1, wherein the fineness of each component after being respectively ground in the step (1) is 10% -16% of the screen residue with the fineness of 80 μm.
3. The method for preparing the silicate-sulphoaluminate composite system clinker by using the waste residue as claimed in claim 1, wherein the calcination in the step (2) is carried out in a high-temperature calciner, a rotary kiln, a vertical kiln or a tunnel kiln.
4. The method for preparing the silicate-sulphoaluminate composite system clinker by using the waste residue as claimed in claim 1, wherein the material in the step (2) is cooled to a temperature 0-60 ℃ higher than the room temperature within 20-30 minutes.
5. The method for preparing the silicate-sulphoaluminate composite system clinker by using the waste slag as claimed in claim 1, wherein the clinker fired in the step (2) is cooled by using an electric fan or a grate cooler.
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| CN111825352A (en) * | 2019-05-31 | 2020-10-27 | 尧柏特种水泥技术研发有限公司 | Moderate heat portland cement produced by composite clinker |
| CN112624641B (en) * | 2020-12-25 | 2022-09-20 | 武汉理工大学 | Method for completely recycling phosphate tailings without waste residues |
| CN113788636A (en) * | 2021-09-18 | 2021-12-14 | 北京金隅通达耐火技术有限公司 | Titanium-based aluminate cement and preparation method thereof |
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| CN105347707B (en) * | 2015-10-30 | 2018-08-24 | 中国建筑材料科学研究总院 | Anti-erosion low-calcium silicate cement and preparation method thereof |
| CN107540251A (en) * | 2017-09-19 | 2018-01-05 | 嘉华特种水泥股份有限公司 | A kind of commerical ready-mixed concrete clinker and preparation method thereof |
| CN107601924A (en) * | 2017-09-25 | 2018-01-19 | 中国葛洲坝集团水泥有限公司 | A kind of modified portland cement clinker and preparation method thereof |
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