CN108793785B - Low-temperature preparation method of sulfosilicate-belite-sulphoaluminate cement - Google Patents
Low-temperature preparation method of sulfosilicate-belite-sulphoaluminate cement Download PDFInfo
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- CN108793785B CN108793785B CN201810818378.0A CN201810818378A CN108793785B CN 108793785 B CN108793785 B CN 108793785B CN 201810818378 A CN201810818378 A CN 201810818378A CN 108793785 B CN108793785 B CN 108793785B
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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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- 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
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Abstract
The invention discloses a low-temperature preparation method of a sulfosilicate-belite-sulphoaluminate cement, which comprises the following steps: (1) putting the raw materials into a planetary ball mill, uniformly mixing and grinding; wherein, the raw materials comprise an aluminum-silicon raw material, an aluminum raw material, a calcium raw material, a silicon raw material and industrial gypsum; (2) pressing the mixed raw materials in the step (1) into cakes, placing the cakes in a high-temperature electric furnace, calcining at the temperature of 700-1200 ℃, and then taking out and quenching; (3) grinding the product obtained in the step (2); (4) and (4) uniformly mixing the product obtained in the step (3) with dihydrate gypsum, and grinding to prepare the cement. The method directly utilizes the common wastes containing the intermediate product phase gehlenite and other aluminates as raw materials, and the raw materials do not need modification or other treatment, thereby saving the treatment cost and improving the utilization rate of the raw materials. Greatly reduces the early cost and solves the environmental problem caused by industrial waste residue.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a method for preparing a sulfosilicate-belite-sulphoaluminate cement clinker by using an intermediate product at a low temperature and a product thereof.
Background
As a building material with the largest consumption, the cement plays an important role in the progress of human society and the development of social economy, and simultaneously generates high energy and resource consumption and greenhouse gas emission. The calcium sulphoaluminate cement has high early strength and high later strength, and also has the advantages of permeability resistance, frost resistance, corrosion resistance and the like; meanwhile, the calcium sulphoaluminate has high hydration activity and can form a large amount of ettringite (AFt), C-S-H and Aluminum Hydroxide (AH) in early stage3) The early strength of the cement is greatly improved by the gel.
Calcium sulfosilicate mineral, as an intermediate transition phase in the calcination of sulphoaluminate cement clinker, has been considered as a mineral with low hydration activity and even inert, with a formation temperature in the range 1050 ℃ -1200 ℃. The calcination temperature of the sulphoaluminate cement clinker is 1250 ℃ or above, and at the temperature, calcium sulphosilicate minerals can be thoroughly decomposed to form belite and anhydrite. Recent studies have shown that calcium sulfosilicate minerals exhibit high hydration activity in sulphoaluminate cement systems, resulting in a substantial improvement in the mid-term strength of sulphoaluminate cements.
The calcination temperature of the sulphoaluminate cement clinker is above 1250 ℃ in order to ensure that the sulphoaluminate waterThe presence of calcium sulfosilicate minerals in the clinker, which is generally required to promote calcium sulfosilicate formation at secondary calcination temperatures, increases to some extent the CO of the sulfosilicate-belite-sulphoaluminate cement2Emissions and energy consumption.
The existing method for preparing calcium sulfoaluminate relates to a method for synthesizing sulphoaluminate cement, such as Chinese patent application with application number of 201510066039.8, which is characterized in that the sulphoaluminate cement contains 5-35% by mass of calcium sulfoaluminate minerals, raw materials are calcined according to a proper calcination system, then secondary calcination is carried out according to set calcination temperature and heat preservation time, and cement clinker after secondary calcination is mixed with gypsum and ground to form the sulphoaluminate cement. The method has the disadvantages of high primary calcination temperature, complex secondary calcination procedure, high energy consumption and sulfur pollution.
For example, the Chinese patent application with the application number of 201710400866.5 discloses a preparation method of calcium sulfosilicate-sulphoaluminate cement, limestone and phosphogypsum are taken as main raw materials and are calcined at the temperature of 1050-.
The prior art has the following defects:
1) the calcination temperature of the sulphoaluminate is higher, so that a sulphosilicate-belite-sulphoaluminate ternary system cannot be formed by one-time calcination;
2) in the case of high-temperature calcination, decomposition of sulfates and thiosilicates, with SO2Sulfur pollution is caused by the emission of sulfur;
3) the decomposition of the sulfosilicate is caused under the condition of high-temperature calcination, secondary calcination is needed, the procedure is complex, and the industrial production is difficult;
4) low-temperature calcination of phosphogypsum promotes the formation of calcium sulfosilicate and reduces the reaction temperature. On one hand, the phosphogypsum is decomposed to generate sulfur pollution, on the other hand, the phosphogypsum is decomposed by needing an additive to promote the decomposition, and the cost is higher.
Disclosure of Invention
The invention aims to provide a low-temperature preparation method of a sulfosilicate-belite-sulphoaluminate cement, which aims to solve the problems of high calcination temperature and complex procedure in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low-temperature preparation method of a sulfosilicate-belite-sulphoaluminate cement comprises the following steps:
(1) putting the raw materials into a planetary ball mill, uniformly mixing and grinding; wherein, the raw materials comprise an aluminum-silicon raw material, an aluminum raw material, a calcium raw material, a silicon raw material and industrial gypsum;
(2) pressing the mixed raw materials in the step (1) into cakes, placing the cakes in a high-temperature electric furnace, calcining at the temperature of 700-1200 ℃, and then taking out and quenching;
(3) grinding the product obtained in the step (2);
(4) and (4) uniformly mixing the product obtained in the step (3) with dihydrate gypsum, and grinding to prepare the cement.
In the step (1), the raw materials comprise the following components in percentage by mass: aluminum-silicon material: aluminum raw materials: calcium raw materials: silicon raw material: 18.23-24.56% of industrial gypsum: 6.09-23.76: 35.86-51.56: 11.23-12.47: 6.72 to 12.91.
In the step (1), the aluminum-silicon raw material waste aluminum silicate refractory material is bauxite, high-alumina cement and CaO-Al2O3Based on one of the refining slag, the calcareous material is limestone, the siliceous material is coal gangue, and the industrial gypsum is industrial waste gypsum such as desulfurized gypsum and the like.
In the step (2), the mixed raw materials are pressed into cakes under the pressure of 2-6 MPa.
In the step (2), the temperature in the high-temperature electric furnace is raised to 700-1200 ℃ and then is kept for 1-3 h.
In the step (3), the powder is ground until the particles can completely pass through a square-hole sieve with the aperture of 80 mu m, and the specific surface area of the powder reaches 350-420 m2/Kg。
Has the advantages that: the method directly utilizes the common wastes containing the intermediate product phase gehlenite and other aluminates as raw materials, and the raw materials do not need modification or other treatment, thereby saving the treatment cost and improving the utilization rate of the raw materials. Greatly reduces the early cost and solves the environmental problem caused by industrial waste residue. In addition, the invention does not need secondary calcination, does not generate a large amount of carbon dioxide, increases the environmental pressure, and has low calcination temperature and low energy consumption. Therefore, the invention is a low-carbon and green preparation method.
Drawings
Figure 1 is an XRD analysis of the product of example 1.
Detailed Description
The invention relates to a low-temperature preparation method of a sulfosilicate-belite-sulphoaluminate cement, which comprises the following steps:
(1) putting the raw materials into a planetary ball mill, uniformly mixing and grinding; wherein, the raw materials comprise an aluminum-silicon raw material, an aluminum raw material, a calcium raw material, a silicon raw material and industrial gypsum; the mass ratio of the raw materials is as follows: aluminum-silicon material: aluminum raw materials: calcium raw materials: silicon raw material: 18.23-24.56% of industrial gypsum: 6.09-23.76: 35.86-51.56: 11.23-12.47: 6.72-12.91; wherein the aluminum-silicon raw material is waste aluminum silicate refractory material, and the aluminum raw material is bauxite, high-alumina cement and CaO-Al2O3Based on one of the refining slag, the calcareous material is limestone, the siliceous material is coal gangue, and the industrial gypsum is industrial waste gypsum such as desulfurized gypsum and the like.
(2) Pressing the mixed raw materials in the step (1) into cakes under the pressure of 2-6MPa, placing the cakes in a high-temperature electric furnace, heating to 700-1200 ℃, preserving heat for 1-3 h, and taking out for quenching;
(3) grinding the product obtained in the step (2) until the particles of the product can completely pass through a square-hole sieve with the aperture of 80 mu m, and the specific surface area reaches 350-420 m2/Kg；
(4) And (4) uniformly mixing the product obtained in the step (3) with dihydrate gypsum, and grinding to prepare the cement.
The main chemical components of part of the raw materials used in the present invention are shown in table 1.
Table 1 part of raw materials main chemical composition (wt%)
The invention is further illustrated by the following specific examples.
Example 1
The raw material formulation is shown in table 2:
table 2 example 1 raw material ratio
The method comprises the following specific steps:
1) mixing materials: weighing the raw materials according to the mass ratio of the table 2, placing the raw materials into a planetary ball mill, grinding for 120min, and pressing under the pressure of 6MPa to prepare a cake;
2) and (3) calcining: putting the product obtained in the step 1) into a high-temperature electric furnace, heating to 700 ℃, preserving heat for 3 hours, and quenching;
3) sieving: the powder is ground to the extent that the particles can pass through a square-hole sieve with the pore diameter of 80 μm completely, and then XRD test is carried out, as shown in figure 1.
Example 2
The raw material formulation is shown in table 3:
table 3 example 2 raw material ratio
The method comprises the following specific steps:
1) mixing materials: weighing the raw materials according to the mass ratio of the table 3, placing the raw materials into a planetary ball mill, grinding for 60min, and pressing under the pressure of 6MPa to prepare a cake;
2) and (3) calcining: crushing the cooled block sample, placing the crushed block sample in a high-temperature furnace, calcining at 950 ℃ and preserving heat for 2 hours, taking out the block sample for quenching, and grinding the block sample by using a ball mill to obtain sulphoaluminate cement clinker;
3) and (3) testing the strength: the clinker and the dihydrate gypsum are mixed evenly and ground to prepare cement, and the cement is subjected to flexural strength, compressive strength and flexural strength tests for 3d and 28d, as shown in Table 4.
Table 4 example 2 strength properties testing
Example 3
The raw material formulation is shown in table 5:
TABLE 5 example 3 raw material ratio
The method comprises the following specific steps:
1) mixing materials: weighing the raw materials according to the mass ratio of Table 5, placing the raw materials into a planetary ball mill, grinding for 60min, and pressing under the pressure of 6MPa to prepare a cake;
2) and (3) calcining: crushing the cooled block sample, placing the crushed block sample in a high-temperature furnace, calcining at 1100 ℃ and keeping the temperature for 1.5h, taking out the block sample for quenching, and grinding the block sample by using a ball mill to obtain sulphoaluminate cement clinker;
3) and (3) testing the strength: the clinker and the dihydrate gypsum are mixed evenly and ground to prepare cement, and the cement is subjected to 3d and 28d flexural strength and compressive strength tests, as shown in Table 6.
Table 6 example 3 strength properties testing
The results show that: the required mineral C is formed by XRD analysis at the temperature of 700 plus material 1100 ℃ and the temperature is kept for 20min-3h5S2$ and C4A3$ 3; the 28d bending resistance is 7.25MPa and the compression resistance is 56.59MPa through a strength test.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A low-temperature preparation method of a sulfosilicate-belite-sulphoaluminate cement is characterized by comprising the following steps: the method comprises the following steps:
（1) Putting the raw materials into a planetary ball mill, uniformly mixing and grinding; wherein, the raw materials comprise an aluminum-silicon raw material, an aluminum raw material, a calcium raw material, a silicon raw material and industrial gypsum; the aluminum-silicon raw material waste aluminium silicate refractory material is bauxite, high-alumina cement and CaO-Al2O3Based on one of the refining slag, the calcareous raw material is limestone, the siliceous raw material is coal gangue, and the industrial gypsum is industrial waste gypsum;
(2) pressing the mixed raw materials in the step (1) into cakes, placing the cakes in a high-temperature electric furnace, calcining at the temperature of 700-1200 ℃, and then taking out and quenching;
(3) grinding the product obtained in the step (2);
(4) and (4) uniformly mixing the product obtained in the step (3) with dihydrate gypsum, and grinding to prepare the cement.
2. The low temperature process for the preparation of a sulphosilicate-belite-sulphoaluminate cement according to claim 1, wherein: in the step (1), the raw materials comprise the following components in percentage by mass: aluminum-silicon material: aluminum raw materials: calcium raw materials: silicon raw material: industrial gypsum = 18.23-24.56: 6.09-23.76: 35.86-51.56: 11.23-12.47: 6.72 to 12.91.
3. The low temperature process for the preparation of a sulphosilicate-belite-sulphoaluminate cement according to claim 1, wherein: in the step (2), the mixed raw materials are pressed into cakes under the pressure of 2-6 MPa.
4. The low temperature process for the preparation of a sulphosilicate-belite-sulphoaluminate cement according to claim 1, wherein: in the step (2), the temperature in the high-temperature electric furnace is raised to 700-1200 ℃ and then is kept for 1-3 h.
5. The low temperature process for the preparation of a sulphosilicate-belite-sulphoaluminate cement according to claim 1, wherein: in the step (3), the powder is ground until the particles can completely pass through a square-hole sieve with the aperture of 80 mu m, and the specific surface area of the powder reaches 350-420 m2/Kg。
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| CN110078393B (en) * | 2019-05-15 | 2022-01-11 | 盐城工学院 | Method for preparing calcium sulfosilicate-sulphoaluminate cement at low temperature |
| CN110078394A (en) * | 2019-05-15 | 2019-08-02 | 盐城工学院 | Low temperature preparation sulphur calcium silicates-belite sulphoaluminate cement clinker method |
| CN110128038A (en) * | 2019-05-15 | 2019-08-16 | 盐城工学院 | Tricalcium silicate-dicalcium silicate-calcium sulphoaluminate cement and its low temperature preparation method |
| CN110194604A (en) * | 2019-05-15 | 2019-09-03 | 盐城工学院 | Tricalcium silicate-sulphur calcium silicates-sulphate aluminium cement and its low temperature preparation method |
| CN113277758A (en) * | 2021-05-27 | 2021-08-20 | 江苏省沙钢钢铁研究院有限公司 | Preparation method of low-cost solid waste based sulphoaluminate cement |
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| CN106966617A (en) * | 2017-04-01 | 2017-07-21 | 盐城工学院 | The method of easy fired belite aluminium sulfate sulphur ferrous aluminate sulphur calcium silicate cement clinker |
| CN107021654A (en) * | 2017-05-31 | 2017-08-08 | 重庆大学 | A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof |
| CN107721214A (en) * | 2017-09-30 | 2018-02-23 | 北京工业大学 | A kind of high ferrous aluminate belite sulphoaluminate cement clinker and preparation method thereof |
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| CN106904848A (en) * | 2017-04-01 | 2017-06-30 | 盐城工学院 | The method and its product of easy fired belite calcium sulphoaluminate sulphur calcium silicate cement |
| CN106966617A (en) * | 2017-04-01 | 2017-07-21 | 盐城工学院 | The method of easy fired belite aluminium sulfate sulphur ferrous aluminate sulphur calcium silicate cement clinker |
| CN107021654A (en) * | 2017-05-31 | 2017-08-08 | 重庆大学 | A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof |
| CN107721214A (en) * | 2017-09-30 | 2018-02-23 | 北京工业大学 | A kind of high ferrous aluminate belite sulphoaluminate cement clinker and preparation method thereof |
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