RAPID-SETTING AND HARDENING, HIGH-BELITE SULFOALUMINATE CEMENT CLINKER AS WELL AS APPLICATION AND PRODUCTION PROCESS THEREOF

Abstract

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 C.sub.4A.sub.3S 3% to 9% by weight of C.sub.4AF, 37% to 47% by weight of C.sub.2S, 0.5% to 4.6% by weight of f-Ca and 14% to 26.3% by weight of CaSO.sub.4. The chemical compositions of the clinker are 12.9% to 16.1% by weight of SiO.sub.2, 12% to 19% by weight of Al.sub.2O.sub.3, 1% to 3% by weight of Fe.sub.2O.sub.3, 49% to 54% by weight of CaO and 12% to 18.43% by weight of SO.sub.3. 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.

Claims

1. A rapid-hardening high-belite calcium sulfoaluminate cement clinker, comprising the following major constituent components: C.sub.4A.sub.3S, C.sub.4AF, C.sub.2S and CaSO.sub.4, 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 C.sub.4A.sub.38, 3% to 9% by weight of C.sub.4AF, 37% to 47% by weight of C.sub.2S, 0.5% to 4.6% by weight of f-CaO and 14% to 26.3% by weight of CaSO.sub.4, 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.TiO.sub.2, or Na.sub.2SO.sub.3 ,or K.sub.2SO.sub.3 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 SiO.sub.2, 12% to 19% by weight of Al.sub.2O.sub.3, 1% to 3% by weight of Fe.sub.2O.sub.3, 49% to 54% by weight of CaO and 12% to 18.43% by weight of SO.sub.3, 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 TiO.sub.2, or Na.sub.2O, or K.sub.2O 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 Al.sub.2O.sub.3.

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 CaSO.sub.4, or any mixture thereof; the type and replacement ratio is controlled to ensure that said clinker contains 12% to 18.43% by weight of SO.sub.3.

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 m.sup.2/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 Li.sub.2CO.sub.3 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 Li.sub.2CO.sub.3 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.

Description

DESCRIPTION OF DRAWINGS

[0061] FIG. 1 is the flow chart of the manufacturing process of rapid-hardening high-belite calcium sulfoaluminate cements.

[0062] In FIG. 1, the manufacturing process of rapid-hardening high-belite calcium sulfoaluminate cement clinker is illustrated by taking the examples of the clinker, which is manufactured by using 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; the manufacturing process of rapid-hardening high-belite calcium sulfoaluminate cement is illustrated by taking the examples of the cement, which is manufactured by mixing and grinding 26% to 97% by weight of the clinker, 3% to 19% by weight of anhydrite and 0% to 55% by weight of GBF slag.

EXAMPLES

[0063] The following examples illustrate the embodiments of the present invention.

[0064] Examples 1 to 6 give the proportion of raw materials for manufacturing clinkers.

[0065] (1) Preparation of raw meal. Table 1 gives the chemical compositions of raw materials. Limestone, fly ash and FGD gypsum are prepared in the proportions given in Table 2, Limestone is ground in a raw mill and is then conveyed, along with fly ash and FGD gypsum, to an air separator. After air separation, the raw materials with proper particle sizes are homogenized to yield raw meal, and the rest of the raw materials are conveyed back to the raw mill. In the process, fly ash and RID gypsum do not go to the raw mill before air separation, and the production of the raw mill, therefore greatly increases, leading to the reductions in both power consumption and abrasion of milling balls.

TABLE-US-00001 TABLE 1 Chemical compositions by weight of raw materials. LOSS SiO.sub.2 Al.sub.2O.sub.3 Fe.sub.2O.sub.3 CaO MgO SO.sub.3 Limestone (wt. %) 41.57 3.25 1.09 0.69 49.2 3.50 0.00 FGD gypsum (wt. %) 21.10 1.84 0.84 1.42 32.69 2.36 39.00 Fly ash (wt. %) 2.31 47.15 34.21 6.21 3.83 1.50 0.95

TABLE-US-00002 TABLE 2 Proportions of raw materials for manufacturing rapid- hardening high-belite calcium sulfoaluminate cement Example Example Example Example Example Example 1 2 3 4 5 6 Limestone (wt. %) 62.0 33.0 35.0 55.3 52.0 62.0 Fly ash (wt. %) 13.5 24.0 20.0 25.7 28.0 10.5 FGD gypsum (wt. %) 24.5 43.0 45.0 19.0 20.0 27.5

[0066] (2) Manufacturing of clinker: the raw meal prepared as in (1) is calcined at a temperature of 1300 C.50 C. in a rotary kiln with preheater to yield clinker. Calcination in a rotary kiln generates a small amount of SO.sub.2 due to the presence of reductive gas. SO.sub.2, along with other gases, goes into a preheater and then reacts with the feeding raw meal, preventing the escape of SO.sub.2. As the decrease in clinkering temperature and coal consumption, the formation and emission of nitrogen oxides are reduced. This is good for the accordance with environmental guidelines.

[0067] (3) Manufacturing of cement: the cement is made by mixing clinker, anhydrite and GBF slag in a proper proportion and grinding into powder with a specific surface area of 450 m.sup.2/kg (Blaine value).

[0068] The flow chart of the manufacturing process is given in FIG. 1.

[0069] The flowability, water demand, setting times and compressive and flexural strengths of the clinkers are measured in accordance with Chinese standard GB 20472-2006 Calcium sulfoaluminate cements. Table 3 lists the results of the clinkers from examples 1 to 6.

TABLE-US-00003 TABLE 3 Physical and mechanical properties of the rapid-hardening high-belite calcium sulfoaluminate cement clinkers Example Example Example Example Example Example 1 2 3 4 5 6 Water/cement ratio 0.52 0.50 0.50 0.49 0.48 0.51 Flowability (mm) 171 168 167 171 169 166 Blaine value (m.sup.2/kg) 474 479 471 473 472 475 Water demand (%) 31.00 30.00 29.80 29.60 29.20 31.00 Initial setting time (min) 9 13 12 13 16 12 Final setting time (min) 13 16 14 16 21 15 Flexural/ 2 h 2.7/12.8 2.6/11.3 1.9/8.2 4.6/20.5 4.3/20.3 1.8/8.7 compressive 4 h 4.0/17.2 3.1/15.0 2.8/13.0 4.4/23.9 4.4/23.1 2.8/13.1 strength 1 d 6.5/39.8 5.4/33.4 5.4/30.2 6.5/40.2 6.1/38.3 5.3/27.9 (MPa) 3 d 6.6/50.7 5.9/36.5 6.7/36.6 6.5/46.0 6.0/41.6 5.6/33.8 7 d 6.8/51.0 6.0/38.6 6.8/39.4 6.7/48.0 7.2/51.5 6.2/38.2 28 d 7.0/60.0 7.1/54.8 6.7/47.1 7.0/65.2 7.3/67.2 6.4/45.4

[0070] The initial setting times of the clinkers of the examples are all shorter than 16 minutes, and the final setting times are all shorter than 40 minutes. The maximum early compressive strength at 2 hours reaches 20.5 MPa. The experimental results indicate that the clinkers of the present invention have the feature of rapid hardening and have higher compressive and flexural strengths than calcium sulfoaluminate cement clinkers.

[0071] Examples 7 to 16 give the experimental results of the chemical compositions of the clinkers.

[0072] The rapid-hardening high-belite calcium sulfoaluminate cement clinkers of the present invention comprise the following major constituent phases: C.sub.4A.sub.3S, C.sub.4AF, C.sub.2S and CaSO.sub.4, and the clinkers are characterized in containing 0.5% to 4.6% by weight of f-CaO. Table 4 gives the proportions of the constituent phases and the modulus values of the clinkers. Table 5 gives the chemical composition of the clinkers. Table 6 gives the physical and mechanical properties of the clinkers.

TABLE-US-00004 TABLE 4 Proportions of the constituent phases and modulus values of the rapid- hardening high-belite calcium sulfoaluminate cement clinkers. Example Example Example Example Example Example Example Example Example Example 7 8 9 10 11 12 13 14 15 16 Proportions of constituent phases (percentage by weight) C.sub.4A.sub.3S 35.00 20.53 20.93 27.39 20.29 33.67 22.81 32.94 20.98 33.27 C.sub.4AF 5.11 8.00 7.05 7.45 9.00 3.00 3.04 4.77 8.06 4.99 C.sub.2S 43.31 45.52 47.00 37.0 43.68 45.20 44.54 44.20 43.68 42.71 f-CaO 0.60 3.88 3.89 3.69 4.35 1.17 2.74 1.43 4.60 0.50 CaSO.sub.4 14.55 20.81 20.72 20.62 20.86 14.79 26.30 14.36 20.71 16.29 Minor phases 1.43 1.26 0.41 3.85 1.82 2.17 0.57 2.30 1.97 2.24 Modulus values Cm 1.02 1.21 1.21 1.22 1.23 1.13 1.18 1.14 1.30 1.01 P 1.34 0.69 0.71 0.88 0.68 1.29 0.62 1.30 0.71 1.20

TABLE-US-00005 TABLE 5 Chemical composition of the rapid-hardening high-belite calcium sulfoaluminate cement clinkers. Example Example Example Example Example Example Example Example Example Example 7 8 9 10 11 12 13 14 15 16 Chemical composition (percentage by weight) SiO.sub.2 15.09 15.86 16.1 12.90 15.22 15.75 15.52 15.40 15.22 14.88 Al.sub.2O.sub.3 19.00 12.00 12.00 15.33 12.09 17.56 12.10 17.56 12.24 17.77 Fe.sub.2O.sub.3 1.68 2.63 2.32 2.45 3.00 1.00 1.00 1.57 2.65 1.64 CaO 50.01 54.00 53.32 49.78 52.99 49.00 52.35 50.42 52.99 49.54 SO.sub.3 13.11 14.91 14.91 15.69 14.91 13.08 18.43 12.00 14.91 13.91 Minor oxides 1.11 0.60 1.35 3.85 1.79 3.61 0.60 3.05 1.99 2.26 Modulus values Cm 1.02 1.21 1.21 1.22 1.23 1.13 1.18 1.14 1.30 1.01 P 1.34 0.69 0.71 0.88 0.68 1.29 0.62 1.30 0.71 1.20

TABLE-US-00006 TABLE 6 Physical and mechanical properties of the rapid-hardening high-belite calcium sulfoaluminate cement clinkers. Example Example Example Example Example Example Example Example Example Example 7 8 9 10 11 12 13 14 15 16 Water/cement ratio 0.47 0.52 0.53 0.51 0.54 0.48 0.52 0.49 0.55 0.47 Flowability (mm) 167 172 167 175 171 168 165 170 167 173 Blaine value (m.sup.2/kg) 472 470 480 473 474 480 472 480 471 480 Water demand (%) 29.00 31.00 31.20 29.20 32.00 29.20 30.20 29.80 34.00 28.60 Setting Initial 16 9 9 10 7 13 11 13 7 18 time (min) Final 20 12 14 14 11 17 14 17 10 23 Flexural/ 2 h 4.3/23.5 1.3/5.5 1.3/5.0 3.4/14.2 1.3/3.9 4.0/19.1 1.5/6.2 3.8/17.0 1.1/3.7 4.1/20.7 compressive 4 h 4.5/27.6 2.4/11.1 2.5/11.0 3.9/19.5 2.3/10.6 4.3/25.6 2.7/12.4 4.2/21.7 2.3/10.1 4.5/25.6 Strength 1 d 6.4/40.7 4.5/25.1 4.4/24.6 5.8/38.7 4.4/24.8 6.2/38.5 4.9/27.0 5.8/35.9 4.2/22.6 6.3/40.1 (MPa) 3 d 6.6/44.6 4.7/29.6 4.6/30.2 5.9/45.4 4.5/28.9 6.3/42.8 5.1/32.4 6.0/40.2 4.5/28.6 6.3/42.8 7 d 7.6/55.6 5.6/38.0 5.5/37.3 6.9/51.9 5.4/37.1 7.3/53.1 6.0/36.6 7.0/48.7 5.2/34.8 7.4/52.2 28 d 7.8/73.0 6.2/44.5 6.2/43.2 7.1/60.7 6.0/42.8 7.5/69.3 6.3/44.3 7.0/64.6 6.0/42.2 7.7/70.0

[0073] The maximum 28-day compressive strength of the clinkers of the examples reaches 73 MPa, which is much higher than the published experimental results of the other existing high-belite calcium sulfoaluminate cement clinkers of low aluminum and high silicon.

[0074] Examples 17 to 35 illustrate the chemical compositions and the physical and mechanical properties of rapid-hardening high-belite calcium sulfoaluminate cements. In Examples 17 to 35, the clinker of Example 7 is used, and the cements are manufactured by the aforementioned method. Table 7 gives the chemical compositions of CaSO.sub.4 sources and supplementary cementitious materials, which are added in step (2) of the manufacturing process. Tables 8 to 10 give the proportions of the cement components and the physical and mechanical properties of the cements of Examples 17 to 35. The expansion of the cements is measured in accordance with Chinese standard GB 23439-2009 Expansive agents for concrete.

TABLE-US-00007 TABLE 7 Chemical compositions of anhydrite and GBF slag and their alternatives. Chemical composition Loss SiO.sub.2 Al.sub.2O.sub.3 Fe.sub.2O.sub.3 CaO MgO SO.sub.3 TiO.sub.2 Sum Anhydrite 6.02 0.94 0.30 0.12 38.95 1.55 51.74 99.62 FGD gypsum 19.42 1.07 0.67 1.04 32.80 1.80 42.87 99.67 Hemihydrate gypsum 9.17 1.26 1.05 0.17 38.07 4.04 45.88 99.64 Phosphogypsum 19.41 2.17 3.60 0.96 32.92 1.24 40.34 100.64 Fluorgypsum 3.04 0.52 0.21 0.10 41.93 0.24 53.42 99.46 Gypsum 22.31 0.82 0.29 0.15 32.49 3.01 40.25 99.32 GBF slag 1.57 33.35 15.40 1.11 39.27 8.02 95.58 Steel slag 0.52 12.39 5.07 26.66 37.02 10.58 91.20 Tailing of iron ore 2.72 72.73 4.86 12.75 3.30 2.01 0.66 99.03 Limestone 41.61 3.60 1.23 0.50 49.87 2.51 99.32 Dolomite 46.29 0.12 0.53 0.19 30.25 21.63 99.01 Sandstone 1.53 93.14 2.31 1.10 0.87 0.11 99.06

TABLE-US-00008 TABLE 8-A Proportion % FGD GBF Fly Steel Tailing of Examples Clinker Anhydrite gypsum Hemihydrate Phosphogypsum Fluorgypsum Gypsum slag ash slag iron ore Limestone 17 97 3 0 0 0 0 0 0 0 0 0 0 18 88 0 10 0 0 0 0 2 0 0 0 0 19 66 15 0 0 0 0 0 19 0 0 0 0 21 66 15 0 0 0 0 0 0 19 0 0 0 22 66 0 0 0 0 0 15 0 0 0 0 0 23 54 15 0 0 0 0 0 31 0 0 0 0 25 54 15 0 0 0 0 0 0 0 0 31 0 26 54 15 0 0 0 0 0 19 0 12 0 0 27 54 0 0 0 15 0 0 31 0 0 0 0 28 54 5 0 10 0 0 0 31 0 0 0 0 29 54 0 0 0 0 15 0 31 0 0 0 0 31 34 16 0 0 0 0 0 50 0 0 0 0 32 26 19 0 0 0 0 0 55 0 0 0 0 Proportion % Blaine Water Setting time Citric w/c Flowability value demand (min) Examples Dolomite Sandstone acid Li.sub.2CO.sub.3 ratio (mm) (m.sup.2/kg) (%) Initial Final 17 0 0 0 0 0.50 167 480 34.2 11 14 18 0 0 0 0 0.48 167 450 31.6 15 18 19 0 0 0 0 0.44 172 480 25.1 50 76 21 0 0 0 0 0.46 174 485 25.8 20 29 22 19 0 0 0 0.47 175 490 26.8 24 31 23 0 0 0 0 0.42 174 473 25.2 11 14 25 0 0 0 0 0.44 168 495 26 14 20 26 0 0 0 0 0.44 175 480 27 12 18 27 0 0 0 0 0.45 175 500 30.6 16 21 28 0 0 0 0 0.47 172 485 30.6 9 11 29 0 0 0 0 0.46 169 500 29.8 12 18 31 0 0 0 0 0.41 175 510 25 21 26 32 0 0 0 0 0.41 171 520 24.8 24 31

TABLE-US-00009 TABLE 8-B 28 d free Restrained expansion % Flexural/compressive strength (MPa) expansion In water In air Examples 2 h 4 h 6 h 1 d 7 d 28 d % 7 d 28 d 21 d 17 5.4/24.1 6.3/33.1 7.2/34.8 7.9/47.sup. 8.1/58.7 8.3/67.9 0.012 0.005 0.009 0.001 18 5.5/25.6 6.8/33.2 7.7/46.4 7.9/51.2 8.0/55.1 8.2/60.6 0.017 0.006 0.012 0.001 19 2.0/4.3 3.5/15.3 4.8/18.3 5.1/30.2 7.3/58.6 9.3/92.7 0.070 0.025 0.050 0.022 21 2.5/7.3 5.1/19.8 5.2/19.5 5.4/31.1 7.1/55.5 8.3/86.6 0.078 0.040 0.054 0.030 22 2.1/5.9 4.8/18.5 5.1/18.9 5.4/31.0 5.8/37.9 6.9/59.9 0.036 0.022 0.028 0.002 23 3.4/11.4 3.7/16.6 4.3/18.8 4.7/20.8 6.4/42.1 8.7/68.3 0.038 0.022 0.028 0.003 25 2.8/9.0 3.1/11.3 3.7/14.0 4.2/17.4 5.5/33.9 6.9/58.9 0.034 0.021 0.027 0.012 26 4.0/12.0 4.7/18.0 5.0/20.0 6.7/31.0 7.8/47.6 8.0/63.0 0.072 0.040 0.055 0.033 27 2.6/8.1 2.9/10.2 3.5/13.6 4.0/16.5 5.3/32.1 6.3/45.1 0.020 0.010 0.015 0.003 28 4.3/17.6 5.0/19.7 5.6/34.9 7.0/37.6 8.0/50.9 8.3/65.0 0.024 0.015 0.020 0.002 29 3.1/12.0 3.4/13.2 3.9/14.0 4.3/19.2 5.8/36.7 7.3/45.6 0.031 0.017 0.024 0.001 31 2.2/5.9 2.4/9.9 2.9/11.0 3.1/13.2 9.6/62.6 11.8/81.7 0.034 0.018 0.026 0.004 32 1.8/4.9 2.2/8.0 2.6/10.2 3.1/12.3 8.3/58.1 10.9/81.0 0.045 0.016 0.025 0.002

[0075] Table 8 gives the examples of rapid-hardening high-belite calcium sulfoaluminate cements, and the data of Examples 20, 24 and 30, which contains additives, are listed in Table 9.

[0076] Table 9 gives the properties of the rapid-hardening high-belite calcium sulfoaluminate cements with additives, including accelerator and/or retarder. The data of Examples 20, 24 and 30 with the additives are listed in Table 9. The experimental results indicate that the addition of the additives has an impressive effect on the properties of the cements.

[0077] The further research reveals that the decrease in the proportion of the clinker has a negative effect on early strength and, however, results in a dramatic increase in later strength. This implies that it is necessary to continue the research on the innovative technology of the invention.

TABLE-US-00010 TABLE 9-A Proportion % FGD GBF Fly Steel Tailing of Examples Clinker Anhydrite gypsum Hemihydrate Phosphogypsum Fluorgypsum Gypsum slag ash slag iron ore Limestone 20 66 15 0 0 0 0 0 0 0 0 0 18.5 24 54 15 0 0 0 0 0 18.7 0 0 0 0 30 54 15 0 0 0 0 0 17.7 10 3 0 0 Proportion % Blaine Water Setting time Citric w/c Flowability value demand (min) Examples Dolomite Sandstone acid Li.sub.2CO.sub.3 ratio (mm) (m.sup.2/kg) (%) Initial Final 20 0 0 0.5 0 0.45 175 498 26.8 22 28 24 0 12 0 0.3 0.43 174 478 25.2 8 10 30 0 0 0.2 0.1 0.43 171 495 26.3 12 18

TABLE-US-00011 TABLE 9-B 28 d free Restrained expansion (%) Flexural/compressive strength (MPa) expansion In water In air Examples 2 h 4 h 6 h 1 d 7 d 28 d (%) 7 d 28 d 21 d 20 2.2/6.1 4.8/18.7 5.0/19.0 5.2/30.9 5.9/40.0 7.8/63.3 0.035 0.036 0.052 0.028 24 4.6/18.3 5.3/20.6 5.9/36.3 7.3/39.2 7.4/46.7 7.5/47.8 0.020 0.019 0.023 0.002 30 4.2/13.1 4.9/19.2 5.2/23.6 6.9/32.8 7.6/45.7 7.6/56.5 0.020 0.024 0.025 0.003

[0078] Table 10 gives more embodiments of high-belite calcium sulfoaluminate cement. In Examples 33 to 35, the clinker proportion in the cements is decreased greatly. Although the decrease in clinker content has a negative effect on the early-stage properties of rapid selling and hardening, the later strength increases dramatically. Without any addition of additives, the 28-day flexural strength can be up to 11.9 MPa to 12.8 MPa, and the 28-day compressive strength can be up to 79.0 MPa to 82.5 MPa. The restrained expansion test reveals that the cements still have a feature of expansion. This provides a chance to further product development and application exploration.

TABLE-US-00012 TABLE 10-A Proportion % FGD GBF Fly Steel Tailing of Examples Clinker Anhydrite gypsum Hemihydrate Phosphogypsum Fluorgypsum Gypsum slag ash slag iron ore Limestone 33 12 17 0 0 0 0 0 71 0 0 0 0 34 8 17 0 0 0 0 0 75 0 0 0 0 35 5 17 0 0 0 0 0 78 0 0 0 0 Proportion % Blaine Water Setting time Citric w/c Flowability value demand (min) Examples Dolomite Sandstone acid Li.sub.2CO.sub.3 ratio (mm) (m.sup.2/kg) (%) Initial Final 33 0 0 0 0 0.40 170 490 26.4 33 46 34 0 0 0 0 0.40 173 495 26.5 38 49 35 0 0 0 0 0.39 171 500 26.6 43 53

TABLE-US-00013 TABLE 10-B 28 d free Restrained expansion (%) Flexural/compressive strength (MPa) expansion In water In air Examples 2 h 4 h 6 h 1 d 7 d 28 d (%) 7 d 28 d 21 d 33 0 0.7/1.2 1.0/2.1 2.2/9.7 9.3/51.3 11.9/79.0 0.11 0.017 0.022 0.002 34 0 0 0.8/1.4 1.8/6.7 9.2/51.6 12.3/81.3 0.12 0.015 0.020 0.002 35 0 0 0.5/0.9 1.3/4.6 8.3/50.6 12.8/82.5 0.10 0.013 0.017 0.001

[0079] The anhydrite in these examples can be partly or fully replaced by FGD gypsum, gypsum, hemihydrate gypsum, phosphogypsum or fluorgypsurn, or by the mixture of two or more of them. The GBF slag can be partly or fully replaced by fly ash, steel slag, tailing of iron ore, limestone, dolomite or sandstone, or by the mixture of two or more of them. The type and replacement ratio need be controlled to ensure that the effect of these materials to the performance of said cement keeps the same. The key issue is that when choosing these materials, the content of effective components should be equivalent. The effective components for set controlling and strength modifying are crucial to the alternatives of anhydrite. The active components should be considered for supplementary cementitious materials. In the rapid-hardening high-belite calcium sulfoaluminate cements, 0.3% by weight of L6CO.sub.3 can be added to shorten setting time and to improve early strength. Li.sub.2CO.sub.3 can be partly or fully replaced by LiOH or LiCl. In the rapid-hardening high-belite calcium sulfoaluminate cements, 0.5% by weight of citric acid can be added to prolong setting time and to improve later strength. Citric acid can be partly or fully replaced by sodium citrate or sodium gluconate.