CN116986830A - Low calcium Portland cement clinker, cement and preparation method - Google Patents
Low calcium Portland cement clinker, cement and preparation method Download PDFInfo
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- CN116986830A CN116986830A CN202311058401.8A CN202311058401A CN116986830A CN 116986830 A CN116986830 A CN 116986830A CN 202311058401 A CN202311058401 A CN 202311058401A CN 116986830 A CN116986830 A CN 116986830A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
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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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a low-calcium silicate cement clinker, cement and a preparation method thereof, wherein the cement clinker comprises the following mineral components in percentage by mass: c (C) 3 S:5~20%，C 2 S:50~60%，C 6 AF 2 :10~20%，C 3 A:0‑7%，C 4 A 3 0.1 to 15 percent. The invention improves C in cement clinker by designing high silicon content 2 S content, further improving the later-stage performance of clinker, and meanwhile, C 4 A 3 Early strength of rapid hydration formation will compensate for C 2 Early hydration activity of clinker caused by increased S contentThe shortage problem leads to good performance development in the early, middle and late stages of cement.
Description
Technical Field
The invention relates to the field of building materials, in particular to low-calcium silicate cement clinker, cement and a preparation method thereof.
Background
The China is a large country for cement production and cement carbon emission, and the cement industry is a second large carbon emission industry in the industrial field of China due to large yield, and faces huge carbon emission reduction pressure. Portland cement is the dominant product in the cement industry in China, and 0.97t of CO is discharged per 1t of cement production on average 2 . The main mineral composition of silicate cement clinker comprises tricalcium silicate (C) 3 S), dicalcium silicate (C 2 S), tetracalcium aluminoferrite (C) 4 AF), tricalcium aluminate (C) 3 A) Etc. Wherein C is 3 The highest S-calcium content and high carbon emission, and greatly reduces C 3 S content, developing novel low-calcium silicate cement clinker to reduce carbon emission of cement industry.
The calcium sulfoaluminate-containing high strength portland cement clinker invented in the patent application 201310138543.5, the mineral component comprises C 3 S 50~75%，C 2 S 2～25％，C 4 AF 2～8％，C 3 A 2~25%，C 4 A 3 2-9%, free calcium oxide (f-CaO) 0.5-3%, periclase (MgO) 1-6%, gypsum (CaSO) 4 ) 0-3%. Are used twice in this patentA calcination procedure, namely, firstly, calcining Portland cement clinker at 1400-1500 ℃, heating the obtained clinker to 1000-1300 ℃ for secondary calcination, and quenching to obtain the clinker; the strengths of clinker 3d and 28d are 42-44 MPa and 65-72 MPa respectively. The invention introduces C into silicate cement clinker by using a two-step firing method 4 A 3 The compressive strength of the clinker can be improved. But the clinker C 3 The S content is higher, so the carbon emission is more, and the secondary sintering process further consumes a large amount of energy.
The invention patent with application number 202210843960.9 provides a high sulfur-resistant silicate cement clinker, the clinker mineral composition comprises C 3 S 35~60%，C 2 S 15~35%，C 3 A 0~7%，C 6 AF 2 10-23%, and preserving the temperature of clinker at 1350-1420 ℃ for 30-40 min. Introduction of C 6 AF 2 The sulfate erosion resistance of the cement clinker is obviously improved, and the cost and the energy consumption of cement production can be reduced. But it only focuses on sulfur resistance and cannot guarantee early and later strength properties required for engineering construction.
Disclosure of Invention
The invention provides a low-calcium silicate cement clinker, cement and a preparation method thereof, wherein the high-silicon content is designed in the silicate cement clinker, so that the later strength of the clinker is ensured; the high iron content is designed, so that the wear resistance of the clinker is improved; introducing sulfur into clinker during sintering process to make sulfur in clinker form C 4 A 3 Exists in the form of $ to ensure the early performance of the clinker.
The technical scheme of the invention is as follows: a low calcium silicate cement clinker comprising the following mineral components in mass percent: c (C) 3 S: 5~20%，C 2 S: 50~60%，C 6 AF 2 : 10~20%，C 3 A: 0-7%，C 4 A 3 $: 0.1~15%。
The raw materials of the cement clinker comprise: iron raw material, silicon aluminum raw material, calcium raw material and gypsum,
the chemical composition of the raw materials is 50% -64% CaO,15% -23% SiO 2 ，3%~15%Al 2 O 3 ，3%~12%Fe 2 O 3 ，0.1%~24%SO 3 。
The iron raw material comprises any one or more of steel slag, iron tailings, laterite and red mud.
The silicon-aluminum raw material comprises any one or more of fly ash, coal gangue, bauxite, clay and sandstone.
The calcareous raw material comprises any one or more of limestone, marble, dolomite, steel slag and carbide slag.
The gypsum comprises any one or more of dihydrate gypsum, anhydrite, desulfurized gypsum and phosphogypsum.
The low-calcium silicate cement comprises, by mass, 95-97% of low-calcium silicate cement clinker and 3-5% of anhydrite.
The preparation method of the low-calcium silicate cement clinker is characterized by comprising the following steps:
(1) Pretreatment of raw materials
Drying the raw materials respectively, crushing and grinding the raw materials respectively to fully grind the raw materials;
(2) Premixing raw materials and tabletting
Uniformly mixing all the raw materials obtained by grinding in the step (1) to obtain raw materials;
(3) Calcination of clinker
Calcining the raw material at a high temperature of 1300-1370 ℃; and taking out the clinker after the calcination, quenching the clinker to room temperature, and cooling the clinker by a fan quenching to obtain the low-calcium silicate cement clinker.
The invention has the following effects:
(1) The invention improves C in cement clinker by designing high silicon content 2 S content, further improving the later-stage performance of clinker, and meanwhile, C 4 A 3 Early strength of rapid hydration formation will compensate for C 2 The problem of insufficient early hydration activity of clinker caused by the increase of S content ensures that cement has good performance development in the early, middle and later stages.
(2) The invention leads the iron phase minerals in the silicate clinker to form C by increasing the iron content in the clinker mineral composition 6 AF 2 The hydration rate is higher than C 4 AF。C 6 AF 2 Hydrating in the presence of gypsum to form ettringite containing iron and compact structure to replenish the space inside the water slurry to raise C 6 AF 2 The content can enable the structure of the cement hydration slurry to be more compact, and the erosion resistance and the wear resistance of the clinker are improved.
Drawings
Fig. 1 is a schematic XRD detection of example 1.
Detailed Description
The present invention is described in detail below in connection with embodiments, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
The raw materials and chemical compositions used in examples 1 to 3 are shown in Table 1.
TABLE 1 chemical composition of raw materials
Example 1:
selecting cement clinker design mineral composition as shown in table 2, preparing raw materials according to the design mineral composition and the material balance principle, and selecting limestone as a calcareous raw material according to the mass percentage, wherein the limestone accounts for 60.54%; bauxite and sandstone are selected as the raw materials of the aluminosilicate, the bauxite and the sandstone respectively account for 6.55 percent and 10.99 percent, the desulfurized gypsum accounts for 0.94 percent and the steel slag accounts for 20.98 percent, 1kg of uniformly mixed raw materials are weighed after fully and uniformly mixed, and the raw materials are ground in a vibration mill until the screen residue of square holes of 0.075mm is lower than 5 percent, so that the powdery cement raw materials are obtained.
Adding 8% of water (i.e. the mass of the water is 8% of the mass of the raw material) into the powdery cement raw material, uniformly stirring, putting into a tablet press, pressing into a disc with the diameter of 235mm, and drying at 105 ℃ for 12h. By adding water, the tablet is convenient to compress.
Taking out the materials, putting the materials into a muffle furnace which is preheated to 900 ℃ for calcining for 30 minutes, so as to lead CaCO in the raw materials 3 Fully decomposing the clinker into CaO, then transferring the CaO into an electric furnace at 1350 ℃ for heat preservation for 1 hour, taking out the clinker, and rapidly cooling the clinker to room temperature by a fan to obtain a clinker block.
Crushing the cooled cement clinker, and grinding the crushed cement clinker by a ball mill until the specific surface area is 400+/-20 m 2 And (3) kg to obtain cement clinker.
TABLE 2 mineral composition of Cement clinker (wt%)
The XRD pattern of the clinker in example 1 is shown in FIG. 1: c can be clearly observed in XRD patterns 3 S、C 2 S、C 6 AF 2 、C 4 A 3 The crystal diffraction peak indicates good formation of clinker minerals.
Example 2:
the design mineral composition of the selected cement clinker is shown in table 3, and raw materials are prepared according to the design mineral composition and the material balance principle in percentage by mass: 61.71% of limestone, 3.83% of bauxite, 12.50% of sandstone, 21.77% of steel slag and 0.19% of anhydrite are fully and uniformly mixed, 1kg of uniformly mixed raw material is weighed, and the raw material is ground in a vibration mill until the screen residue of square holes of 0.075mm is lower than 5%, so as to obtain powdery cement raw material.
The method is characterized in that 8% of water by mass is added into powdery cement raw materials, the raw materials are uniformly stirred and pressed into compact raw material tablets and are sufficiently dried, and the purpose of the step is to promote solid phase reaction in the clinker formation process. Taking out the materials, calcining for 30 minutes at 900 ℃, then transferring to 1350 ℃ for heat preservation for 1 hour, and rapidly cooling the materials to room temperature by a fan.
Crushing the cooled cement clinker, and grinding the crushed cement clinker by a ball mill until the specific surface area is 400+/-20 m 2 And/kg to obtain cement clinker.
TABLE 3 mineral composition of Cement clinker (wt%)
Example 3:
the design mineral composition of the selected cement clinker is shown in table 4, and raw materials are prepared according to the design mineral composition and the material balance principle in percentage by mass: 63.33% of limestone, 6.59% of bauxite, 13.50% of sandstone, 14.71% of steel slag and 1.87% of anhydrite are fully and uniformly mixed, 1kg of uniformly mixed raw material is weighed, and the raw material is ground in a vibration mill until the screen residue of square holes of 0.075mm is lower than 5%, so as to obtain powdery cement raw material.
Adding 8% of water into the powdery cement raw material, uniformly stirring, pressing into compact raw material tablets, and fully drying. Taking out the materials, calcining for 30 minutes at 900 ℃, then transferring to 1350 ℃ for heat preservation for 1 hour, and rapidly cooling the materials to room temperature by a fan.
Crushing the cooled cement clinker blocks, and grinding the crushed cement clinker blocks until the specific surface area is 400+/-20 m 2 And (3) kg to obtain cement clinker.
TABLE 4 mineral composition of Cement clinker (wt%)
Example 4:
cement was prepared from the clinker prepared in examples 1, 2 and 3 in a ratio of clinker to anhydrite=95:5, labeled HFC1, HFC2 and HFC3, and cement mortar strength was tested according to GB/T17671-1999 "cement mortar strength test method", with a mortar ratio of 1:3, molding a mortar test piece by using a test mold with the dimensions of 40mm multiplied by 160 mm. Meanwhile, the reference cement properties, numbered p.o42.5, were compared to observe the properties of the novel clinker. The strength results are shown in Table 5.
TABLE 5
By way of comparison, the cement strengths in examples 1-3 of the present invention were higher than the strength of the P.O42.5 reference cement.
In the cement clinker of the invention, C 3 The S has high gelling activity, and the reduction of the S content directly leads to serious reduction of the strength performance of cement. C (C) 2 Low S early activityBut has better post strength. Calcium sulfoaluminate (C) 4 A 3 Low calcium content and excellent early performance. Formation of C by introduction of sulfur into Portland cement 4 A 3 Will effectively make up for C 3 S content reduction and C 2 The problem of insufficient early strength due to the increased S content. Even if C is introduced 4 A 3 The content should also be controlled to be as low as possible. To ensure stable development of clinker performance, C is further adjusted 6 AF 2 The content of the gelled active iron phase is higher, so that the industrialization wide popularization and application of the low-calcium silicate cement clinker are realized.
In addition, hexacalcium dialuminate (C) 6 AF 2 ) The equal iron phase mineral has high strength and early strength, and has good effects in improving the toughness of silicate cement, sulfate corrosion resistance and the like. By increasing C in Portland cement 6 AF 2 The content can obviously exert the advantages of the composition in aspects of erosion resistance, wear resistance and the like.
Aiming at the contradictory requirements of further calcium reduction, carbon reduction and high performance, the invention simultaneously introduces C 4 A 3 And increase C 2 S and a method for high gel iron phase content, realizes the cooperative development of early and later performances of clinker, and simultaneously prepares the cement clinker with excellent performances such as wear resistance.
Claims (8)
1. A low-calcium silicate cement clinker, characterized in that it comprises the following mineral components in mass percent: c (C) 3 S: 5~20%，C 2 S: 50~60%，C 6 AF 2 : 10~20%，C 3 A: 0-7%，C 4 A 3 $: 0.1~15%。
2. The low-calcium silicate cement clinker according to claim 1, wherein the raw materials of the cement clinker comprise: iron raw material, silicon aluminum raw material, calcium raw material and gypsum,
the chemical composition of the raw materials is 50% -64% CaO,15% -23% SiO 2 ，3%~15%Al 2 O 3 ，3%~12%Fe 2 O 3 ，0.1%~24%SO 3 。
3. A low calcium portland cement clinker according to claim 2, wherein the iron raw material comprises any one or more of steel slag, iron tailings, laterite, red mud.
4. A low calcium portland cement clinker according to claim 2, wherein the aluminous raw material comprises any one or more of fly ash, coal gangue, bauxite, clay, sandstone.
5. A low calcium portland cement clinker according to claim 2, wherein the calcareous raw material comprises any one or more of limestone, marble, dolomite, steel slag, carbide slag.
6. A low calcium silicate cement clinker according to claim 2, wherein the gypsum comprises any one or more of anhydrite, desulfurized gypsum, phosphogypsum.
7. The low-calcium silicate cement is characterized by comprising, by mass, 95% -97% of the low-calcium silicate cement clinker according to any one of claims 1-6 and 3% -5% of anhydrite.
8. A method for preparing the low-calcium silicate cement clinker according to any one of claims 1 to 6, comprising the steps of:
(1) Pretreatment of raw materials
Drying the raw materials respectively, crushing and grinding the raw materials respectively to fully grind the raw materials;
(2) Premixing raw materials and tabletting
Uniformly mixing all the raw materials obtained by grinding in the step (1) to obtain raw materials;
(3) Calcination of clinker
Calcining the raw material at a high temperature of 1300-1370 ℃; and taking out the clinker after the calcination, quenching the clinker to room temperature, and cooling the clinker by a fan quenching to obtain the low-calcium silicate cement clinker.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117585920A (en) * | 2023-11-16 | 2024-02-23 | 西南科技大学 | Low clinker cementitious material and its preparation method and application |
| CN120058250A (en) * | 2025-04-23 | 2025-05-30 | 山东东华科技有限公司 | Cement clinker for high-speed rail and preparation method thereof |
| CN120328891A (en) * | 2025-05-16 | 2025-07-18 | 北京科技大学 | Multi-component solid waste cement clinker and preparation method thereof |
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| CN104788032A (en) * | 2015-04-09 | 2015-07-22 | 中国建筑材料科学研究总院 | Belite cement and preparation method thereof |
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| CN104788032A (en) * | 2015-04-09 | 2015-07-22 | 中国建筑材料科学研究总院 | Belite cement and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117585920A (en) * | 2023-11-16 | 2024-02-23 | 西南科技大学 | Low clinker cementitious material and its preparation method and application |
| WO2025102569A1 (en) * | 2023-11-16 | 2025-05-22 | 中材建设有限公司 | Low-clinker cementing material, and preparation method therefor and use thereof |
| CN120058250A (en) * | 2025-04-23 | 2025-05-30 | 山东东华科技有限公司 | Cement clinker for high-speed rail and preparation method thereof |
| CN120328891A (en) * | 2025-05-16 | 2025-07-18 | 北京科技大学 | Multi-component solid waste cement clinker and preparation method thereof |
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