The invention discloses a rapid-hardening high-belite calcium sulfoaluminate cement clinker and relates generally to a rapid-hardening high-belite calcium sulfoaluminate cement clinker and methods to use and to manufacture the clinker. The clinker of the present invention comprises 20% to 35% by wei
The invention discloses a rapid-hardening high-belite calcium sulfoaluminate cement clinker and relates generally to a rapid-hardening high-belite calcium sulfoaluminate cement clinker and methods to use and to manufacture the clinker. The clinker of the present invention comprises 20% to 35% by weight of C4A3S 3% to 9% by weight of C4AF, 37% to 47% by weight of C2S, 0.5% to 4.6% by weight of f-Ca° and 14% to 26.3% by weight of CaSO4. The chemical compositions of the clinker are 12.9% to 16.1% by weight of SiO2, 12% to 19% by weight of Al2O3, 1% to 3% by weight of Fe2O3, 49% to 54% by weight of CaO and 12% to 18.43% by weight of SO3. It is manufactured by calcining, at a temperature of 1300° C.±50° C. in a rotary kiln, the raw meal, comprising 33% to 62% by weight of limestone, 10.5% to 28% by weight of fly ash, and 19% to 45% by weight of FGD gypsum. A group of rapid-hardening high-strength cements of various strength classes can be manufactured by mixing and grinding 26% to 97% by weight of clinker, 3% to 19% by weight of anhydrite and 0% to 55% by weight of granulated blast furnace slag.
대표청구항▼
1. A rapid-hardening high-belite calcium sulfoaluminate cement clinker, comprising the following major constituent components: C4A3S, C4AF, C2S and CaSO4, wherein said clinker contains 0.5% to 4.6% by weight of f-CaO. 2. The rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim
1. A rapid-hardening high-belite calcium sulfoaluminate cement clinker, comprising the following major constituent components: C4A3S, C4AF, C2S and CaSO4, wherein said clinker contains 0.5% to 4.6% by weight of f-CaO. 2. The rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 1, wherein said clinker comprises 20% to 35% by weight of C4A38, 3% to 9% by weight of C4AF, 37% to 47% by weight of C2S, 0.5% to 4.6% by weight of f-CaO and 14% to 26.3% by weight of CaSO4, and the rest are minor additional components. 3. The rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 2, comprising ≦7% by weight of said minor additional components. 4. The rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 2, wherein said minor additional phases include components comprise MgO, or CaO.TiO2, or Na2SO3 ,or K2SO3 or the mixture of two or more thereof. 5. The rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 1, wherein said clinker comprises the following major constituent components: 12.9% to 16.1% by weight of SiO2, 12% to 19% by weight of Al2O3, 1% to 3% by weight of Fe2O3, 49% to 54% by weight of CaO and 12% to 18.43% by weight of SO3, and the rest are minor additional components. 6. The rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 5, comprising ≦4% by weight of said minor additional components. 7. The rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 5, wherein said minor additional components include MgO, or TiO2, or Na2O, or K2O or the mixture of two or more thereof. 8. A manufacturing method for the rapid-hardening high-belite calcium sulfoaluminate cement clinker, wherein said method includes the following steps: (1) preparing raw materials: calculating the proportions of raw materials according to said components in claim 1, the raw materials include 33% to 62% by weight of limestone, 10.5% to 28% by weight of fly ash and 19% to 45% by weight of flue gas desulfurization (FGD) gypsum;(2) preparing raw meal: grinding and homogenizing the raw materials in (1) to yield a raw meal with a specified fineness;(3) calculating: calcining, in a rotary kiln, the raw meal prepared in (2) at a temperature of 1300° C.±50° C. to produce the clinker. 9. The manufacturing method of claim 8, wherein said limestone is partly or fully replaced by alkaline residue from chlor-alkali industry, or steel slag, or carbide slag, or any mixture thereof; the type and replacement ratio is controlled to ensure that said clinker contains 49% to 54% by weight of CaO. 10. The manufacturing method of claim 8, wherein said fly ash is partly or fully replaced by bauxite, or tailing of bauxite, or coal gangue, or kaolin, or fluidized bed combustion slag, or clay, or any mixture thereof; the type and replacement ratio is controlled to ensure that said clinker contains 12% to 19% by weight of Al2O3. 11. The manufacturing method of claim 8, wherein said FGD gypsum is partly or fully replaced by anhydrite, or gypsum, or hemihydrate gypsum, or phosphogypsum, or fluorgypsum, or aluminum sulfate, or an industry waste rich in CaSO4, or any mixture thereof; the type and replacement ratio is controlled to ensure that said clinker contains 12% to 18.43% by weight of SO3. 12. A rapid-hardening high-belite calcium sulfoaluminate cement, made by mixing and grinding a clinker, a set-controlling strength-modifying agent and a supplementary cementitious material, wherein said cement is characterized in that: (1) said clinker is the rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 1; said set-controlling strength-modifying agent is an anhydrite; said supplementary cementitious material is a granulated blast furnace (GBF) slag;(2) said cement is made by mixing and grinding 26% to 97% by weight of the rapid-hardening high-belite calcium sulfoaluminate cement clinker, 3% to 19% by weight of the anhydrite, and 0% to 55% by weight of the GBF slag;(3) according to the targeted strength class, the proportion of the clinker is determined in the range of 26% to 97% by weight; the proportions of the anhydrite and the GBF slag are tailored within said range as in (2) based on the experimental results of mini grinding mill tests to ensure that said cement has the following properties:initial setting time: 9 minutes to 30 minutes, final setting time: 11 minutes to 40 minutes, 2-hour flexural strength: 1.8 MPa to 4.6 MPa, 2-hour compressive strength: 4.9 MPa to 25.6 MPa, 28-day flexural strength: 6.3 MPa to 11.8 MPa, 28-day compressive strength: 45.1 MPa to 92.7 MPa, 28-day free expansion: 0.012% to 0.078%, 21-day restrained expansion in air: 0.001% to 0.033%, and 28-day restrained expansion in water: 0.009% to 0.055%. 13. The rapid-hardening high-belite calcium sulfoaluminate cement of claim 12, wherein said anhydrite is partly or fully replaced by FGD gypsum, or gypsum, or hemihydrate gypsum, or phosphogypsum, or fluorgypsum, or any mixture thereof. 14. The rapid-hardening high-belite calcium sulfoaluminate cement of claim 12, wherein said GBF slag can be is partly or fully replaced by fly ash, or steel slag, or tailing of iron ore, or limestone, or dolomite, or sandstone, or any mixture thereof. 15. A manufacturing method for a rapid-hardening high-belite calcium sulfoaluminate cement, wherein said method includes comprises the following steps: (1) preparing a raw meal: grinding 33% to 62% by weight of limestone in a raw mill and then mixing with 10.5% to 28% by weight of fly ash and 19% to 45% by weight of FGD gypsum to produce a raw material; air-separating and homogenizing the raw material to yield the raw meal;(2) manufacturing of a clinker: calcining the raw meal at a temperature of 1300° C.±50° C. in a rotary kiln to yield the clinker, said clinker containing 0.5% to 4.6% by weight of f-CaO;(3) manufacturing of a cement: according to the proportions as in (2) of claim 12 and a targeted strength class, selecting the clinker used for manufacturing said cement; with the chemical compositions of the clinker, set-controlling strength-modifying agent and supplementary cementitious material, the proportions of the clinker, set-controlling strength-modifying agent and supplementary cementitious material are designed for mini grinding mill tests; based the experimental results of mini grinding mill tests and experiences, the proportions of clinker, set-controlling strength-modifying agent and supplementary cementitious material, and mixing and grinding the constituents into powder with a specific surface area of ≧450 m2/kg (Blaine value) to produce the cement. 16. The manufacturing method of claim 15, wherein before said mixing and grinding 0.1% to 0.3% by weight of Li2CO3 is added into said cement in order to shorten setting time and to improve early strength. 17. The manufacturing method of claim 15, wherein 0.2% to 0.5% by weight of citric acid is added into said cement in order to prolong setting time and to improve later strength. 18. The manufacturing method of claim 16, wherein said Li2CO3 is partly or fully replaced by LiOH or LiCl. 19. The manufacturing method of claim 17, wherein said citric acid is partly or fully replaced by sodium citrate or sodium gluconate. 20. The high-belite calcium sulfoaluminate cement according to claim 12, made by mixing and grinding a clinker, a set-controlling strength-modifying agent and a supplementary cementitious material, wherein it is characterized in that: the proportions by weight of the rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 1, the anhydrite and the GBF slag are 5% to 12%, 17% to 18% and 71% to 78%, respectively; for the targeted strength class, the proportion of the clinker is determined in the range of 5% to 12% by weight, based on the experimental results of mini grinding mill tests, the proportions of the anhydrite and the GBF slag are tailored within said range in previous paragraph to ensure that said cement has the following properties: initial setting time of ≦43 minutes, final setting time of <53 minutes, 28-day flexural strength of 11.9 MPa to 12.8 MPa, 28-day compressive strength of 79 MPa to 82.5 MPa, 28-day free expansion of 0.10% to 0.12%, 21-day restrained expansion in air of 0.001% to 0.002% and 28-day restrained expansion in water of 0.017% to 0.022%. 21. The rapid-hardening high-belite calcium sulfoaluminate cement clinker of claim 1, wherein said clinker comprises 1.17% to 4.6% by weight of f-CaO.
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