CN111792858A - Dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement and one-time firing method - Google Patents
Dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement and one-time firing method Download PDFInfo
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- CN111792858A CN111792858A CN202010660794.XA CN202010660794A CN111792858A CN 111792858 A CN111792858 A CN 111792858A CN 202010660794 A CN202010660794 A CN 202010660794A CN 111792858 A CN111792858 A CN 111792858A
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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
- C04B7/345—Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
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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
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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
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement and a one-time firing method, which comprises 1 part of limestone, 0.15-0.4 part of silicon dioxide, 0.2-0.5 part of aluminum oxide and 0.15-0.2 part of dihydrate gypsum by mass; the method for firing a cement clinker product comprises the steps of: 1) mixing limestone, silicon dioxide, aluminum oxide and dihydrate gypsum according to a required proportion, placing the mixture into a stirrer, stirring for 6 hours, and fully mixing; 2) pressing the raw material mixture into sheets under 4.5MPa, drying the sheets, putting the dried sheets into a high-temperature furnace, gradually heating the dried sheets to 1150-1200 ℃, preserving the heat for 0.5-1 h, and quickly taking out the dried sheets for cooling; 3) and crushing the cooled clinker pieces in a vibration mill to obtain the cement clinker. The cement calcination technology has the advantages of low temperature requirement, low energy consumption and capacity of reaching the conversion rate of clinker in the finished product by 90 percent.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement, a one-time sintering method and application.
Background
The cement is an important raw material for national infrastructure construction, and has important contribution in the process of national economy and social development, particularly urbanization and modernization. The portland cement has the advantages of easily available raw materials, mature production process, stable performance and the like, and always occupies an absolute dominant position (more than 95%) in various cements. However, silicate cement is very high in resource energy consumption and carbon emission in the manufacturing process, and causes a huge environmental load in the cement industry. The novel clinker system with low emission and low energy consumption is explored, and the novel cement with low emission and low energy consumption which replaces portland cement and is mutually complemented with the portland cement in application is one of effective ways for reducing the resource consumption and emission of the cement industry and lightening the environmental load pressure of the cement industry. Today, a wide variety of cementitious materials, such as alkali-activated cements, geopolymers, sulphoaluminate cements, etc., have been studied and developed, but none of them have matured to be able to replace portland cement in a large amount.
Among these, calcium sulfosilicate minerals, belite and thioaluminate are gradually coming into the field of vision. The new cement aims to combine the rapid early strength characteristic of sulphoaluminate cement with the expected durability of belite cement, and then the calcium sulfosilicate mineral is used for accelerating the middle hydration, so that a product with excellent full-age performance, stable strength and good durability is obtained.
The dicalcium silicate is prepared by compounding calcium oxide and silicon dioxide, and when the temperature reaches 1350-1450 ℃, the silicon dioxide and the calcium oxide are dissolved in a liquid phase and react to generate the dicalcium silicate. It is also one of the 4 main constituent minerals of portland cement clinker, mainly providing the cement with late strength.
Calcium sulfosilicate is a transition mineral formed by the reaction of belite minerals and anhydrite during calcination of a sulfoaluminate cement clinker. The mineral is generally considered to be an inert mineral and its formation is avoided in conventional sulphoaluminate cement synthesis, but it has been found in research that calcium sulphoaluminate hydration in sulphoaluminate cement can significantly stimulate the hydration activity of calcium sulphoaluminate.
The dicalcium silicate-calcium sulfoaluminate-calcium sulfosilicate clinker system is a new system which has development prospect and is newly proposed. The firing temperature of the clinker is reduced by about 200 ℃ compared with that of silicate cement clinker, and the carbon dioxide emission and energy consumption are respectively reduced by about 25% -35% and 10% -15%. The firing temperature is reduced by more than 100 ℃ compared with the sulphoaluminate clinker. The cement has the characteristics of excellent long-term stability of the Portland cement and high early strength of the sulphoaluminate cement. The new system clinker can reduce the production of portland cement clinker to the maximum, and can possibly replace portland cement in application, thereby reducing the pressure of energy, resources and environment in the cement industry to the maximum extent, and having very wide popularization and application prospects.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement, a one-time sintering method and application thereof, the cement calcination technology has low required temperature and low energy consumption, and the conversion rate of clinker in a finished product can reach 90%.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method for once firing the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement is characterized in that the once fired dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement comprises the following components in parts by mass: limestone: 1 part, silica: 0.15-0.4 part of alumina: 0.2-0.5 parts of dihydrate gypsum: 0.15-0.2 part; the method for firing a cement clinker product comprises the steps of:
1) mixing limestone, silicon dioxide, aluminum oxide and dihydrate gypsum according to a required proportion, placing the mixture into a stirrer, stirring for 6 hours, and fully mixing;
2) pressing the raw material mixture into sheets under 4.5MPa, drying the sheets, putting the dried sheets into a high-temperature furnace, gradually heating the dried sheets to 1150-1200 ℃, preserving the heat for 0.5-1 h, and quickly taking out the dried sheets for cooling;
3) and crushing the cooled clinker pieces in a vibration mill to obtain the cement clinker.
In a specific embodiment of the present invention, the limestone comprises the following components in percentage by mass: calcium carbonate is more than or equal to 91.13 percent, aluminum oxide is less than or equal to 1 percent, ferric oxide is less than or equal to 1 percent, calcium oxide is less than or equal to 5.1 percent, water is less than or equal to 0.15 percent, and the granularity of the limestone is 0.5cm-1.5 cm.
In a specific embodiment of the invention, the silica is a chemical reagent product, and comprises the following components in percentage by mass: more than or equal to 99.0 percent of silicon dioxide, less than or equal to 0.1 percent of chloride, less than or equal to 0.5 percent of sulfate and less than or equal to 5 percent of drying weight loss;
in a specific embodiment of the invention, the alumina is a chemical reagent product, and comprises the following components in percentage by mass: more than or equal to 99.0 percent of aluminum oxide, less than or equal to 0.04 percent of ferric oxide, less than or equal to 0.5 percent of sodium oxide and less than or equal to 0.05 percent of silicon dioxide.
In a specific embodiment of the invention, the dihydrate gypsum is a chemical reagent product, and the mass fraction of the dihydrate gypsum is more than or equal to 99.0%.
The invention also aims to provide dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement, which is characterized by being prepared by the method for one-time firing dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement.
The invention also aims to provide application of the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement as a cementing material in the field of construction.
Compared with the prior art, the invention has the following advantages:
1) the calcination temperature of the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement clinker is low, and the energy consumption for preparing the cement clinker can be effectively reduced.
2) The dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement clinker contains a large amount of calcium sulfosilicate minerals, can solve the problem of middle and later strength shrinkage of common sulphoaluminate cement, and shows a growing trend in later strength.
3) The calcine of dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement needs less aluminium components, and low-grade bauxite or aluminium-containing industrial waste can be used for production in industrial production, so that the production cost can be greatly reduced.
4) The calcium sulfosilicate mineral in the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement can be hydrated with sulphoaluminate in a synergistic manner, so that the hydration rate is mutually accelerated, and the high early and medium strength is achieved.
Detailed Description
The technical solution of the present invention is further described below with reference to examples.
Example 1: mixing 71 parts by mass of limestone, 26.5 parts by mass of silicon dioxide, 33 parts by mass of aluminum oxide and 13.2 parts by mass of dihydrate gypsum, and mixing the prepared raw material in a mixer for 6 hours to prepare cement raw material; and calcining the obtained raw material in a high-temperature furnace, heating the high-temperature furnace from room temperature to 1150 ℃, preserving the heat at 1150 ℃ for 30min, taking the clinker out of the high-temperature furnace, and quenching the clinker in air to obtain the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement clinker. Through Rietveld full-spectrum fitting quantitative analysis, the mineral composition of the cement clinker is as follows: calcium sulfoaluminate: 25.36%, calcium sulfosilicate: 30.24%, tricalcium aluminate: 6.38%, gypsum: 7.53 percent of calcium silicate and 30.49 percent of dicalcium silicate.
Example 2: 65 parts by mass of limestone, 25.3 parts by mass of silica, 31.5 parts by mass of alumina and 11.8 parts by mass of dihydrate gypsum are mixed, and then the prepared raw meal is mixed in a mixer for 6 hours to prepare cement raw meal. And calcining the obtained raw material in a high-temperature furnace, heating the high-temperature furnace from room temperature to 1200 ℃, preserving the heat at 1200 ℃ for 30min, taking the clinker out of the high-temperature furnace, and quenching the clinker in the air to obtain the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement clinker. Through Rietveld full-spectrum fitting quantitative analysis, the mineral composition of the cement clinker is as follows: calcium sulfoaluminate: 28.63%, calcium sulfosilicate: 33.51%, tricalcium aluminate: 5.6%, gypsum: 6.27 percent of calcium silicate and 26.53 percent of dicalcium silicate.
Example 3: 68 parts by mass of limestone, 27.1 parts by mass of silicon dioxide, 29.8 parts by mass of aluminum oxide and 12.5 parts by mass of dihydrate gypsum are mixed, and then the prepared raw materials are mixed in a stirrer for 6 hours to prepare cement raw materials; and calcining the obtained raw material in a high-temperature furnace, heating the high-temperature furnace from room temperature to 1200 ℃, preserving heat for 1h at the temperature of 1200 ℃, taking the clinker out of the high-temperature furnace, and quenching the clinker in air to obtain the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement clinker. Through Rietveld full-spectrum fitting quantitative analysis, the mineral composition of the cement clinker is as follows: calcium sulfoaluminate: 30.72%, calcium sulfosilicate: 27.48%, tricalcium aluminate: 5.22%, gypsum: 4.33 percent and dicalcium silicate 32.25 percent.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Variations and modifications in other variations will occur to those skilled in the art upon reading the foregoing description. Not all embodiments are exhaustive. All obvious changes and modifications of the present invention are within the scope of the present invention.
Claims (7)
1. The method for sintering the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement in one step is characterized by comprising the following steps of: the once-fired dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement comprises the following components in parts by mass: limestone: 1 part, silica: 0.15-0.4 part of alumina: 0.2-0.5 parts of dihydrate gypsum: 0.15-0.2 part; the method for firing a cement clinker product comprises the steps of:
1) mixing limestone, silicon dioxide, aluminum oxide and dihydrate gypsum according to a required proportion, placing the mixture into a stirrer, stirring for 6 hours, and fully mixing;
2) pressing the raw material mixture into sheets under 4.5MPa, drying the sheets, putting the dried sheets into a high-temperature furnace, gradually heating the dried sheets to 1150-1200 ℃, preserving the heat for 0.5-1 h, and quickly taking out the dried sheets for cooling;
3) and crushing the cooled clinker pieces in a vibration mill to obtain the cement clinker.
2. The method for primary-firing dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement as claimed in claim 1, wherein: the limestone comprises the following components in percentage by mass: calcium carbonate is more than or equal to 91.13 percent, aluminum oxide is less than or equal to 1 percent, ferric oxide is less than or equal to 1 percent, calcium oxide is less than or equal to 5.1 percent, water is less than or equal to 0.15 percent, and the granularity of the limestone is 0.5cm-1.5 cm.
3. The method for primary-firing dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement as claimed in claim 1, wherein: the silicon dioxide is a chemical reagent product and comprises the following components in percentage by mass: more than or equal to 99.0 percent of silicon dioxide, less than or equal to 0.1 percent of chloride, less than or equal to 0.5 percent of sulfate and less than or equal to 5 percent of drying weight loss.
4. The method for primary-firing dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement as claimed in claim 1, wherein: the aluminum oxide is a chemical reagent product and comprises the following components in percentage by mass: more than or equal to 99.0 percent of aluminum oxide, less than or equal to 0.04 percent of ferric oxide, less than or equal to 0.5 percent of sodium oxide and less than or equal to 0.05 percent of silicon dioxide.
5. The method for primary-firing dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement as claimed in claim 1, wherein: the dihydrate gypsum is a chemical reagent product, and the mass fraction of the dihydrate gypsum is more than or equal to 99.0%.
6. A dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement produced by the method of one-shot dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement as claimed in any one of claims 1 to 5.
7. Use of the dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement of claim 6 as a cementitious material in the construction sector.
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| CN202010660794.XA CN111792858A (en) | 2020-07-10 | 2020-07-10 | Dicalcium silicate-calcium sulfosilicate-sulphoaluminate cement and one-time firing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608047A (en) * | 2020-12-22 | 2021-04-06 | 中国建筑材料科学研究总院有限公司 | Modified sulphoaluminate cement and preparation method and application thereof |
| CN112960929A (en) * | 2021-03-05 | 2021-06-15 | 北京工业大学 | Method for preparing calcium sulfosilicate-dicalcium silicate-calcium sulfoaluminate system from calcium carbide slag raw material and improving later strength of cement |
| CN115849740A (en) * | 2022-12-07 | 2023-03-28 | 中国建筑材料科学研究总院有限公司 | Dicalcium silicate-calcium sulfoaluminate-calcium sulfosilicate cement clinker and preparation process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH685557A5 (en) * | 1993-02-17 | 1995-08-15 | Catrel Technologie Roger John | Cement prodn. |
| CN110078394A (en) * | 2019-05-15 | 2019-08-02 | 盐城工学院 | Low temperature preparation sulphur calcium silicates-belite sulphoaluminate cement clinker method |
| CN110078393A (en) * | 2019-05-15 | 2019-08-02 | 盐城工学院 | A kind of method of low temperature preparation sulphur calcium silicates-sulphate aluminium cement |
-
2020
- 2020-07-10 CN CN202010660794.XA patent/CN111792858A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH685557A5 (en) * | 1993-02-17 | 1995-08-15 | Catrel Technologie Roger John | Cement prodn. |
| CN110078394A (en) * | 2019-05-15 | 2019-08-02 | 盐城工学院 | Low temperature preparation sulphur calcium silicates-belite sulphoaluminate cement clinker method |
| CN110078393A (en) * | 2019-05-15 | 2019-08-02 | 盐城工学院 | A kind of method of low temperature preparation sulphur calcium silicates-sulphate aluminium cement |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608047A (en) * | 2020-12-22 | 2021-04-06 | 中国建筑材料科学研究总院有限公司 | Modified sulphoaluminate cement and preparation method and application thereof |
| CN112960929A (en) * | 2021-03-05 | 2021-06-15 | 北京工业大学 | Method for preparing calcium sulfosilicate-dicalcium silicate-calcium sulfoaluminate system from calcium carbide slag raw material and improving later strength of cement |
| CN115849740A (en) * | 2022-12-07 | 2023-03-28 | 中国建筑材料科学研究总院有限公司 | Dicalcium silicate-calcium sulfoaluminate-calcium sulfosilicate cement clinker and preparation process thereof |
| CN115849740B (en) * | 2022-12-07 | 2024-03-29 | 中国建筑材料科学研究总院有限公司 | Dicalcium silicate-calcium sulfoaluminate-calcium sulfosilicate cement clinker and preparation process thereof |
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Application publication date: 20201020 |