CN116768505A - Ion doping prepared alite-belite-calcium sulfoaluminate cement clinker and method - Google Patents
Ion doping prepared alite-belite-calcium sulfoaluminate cement clinker and method Download PDFInfo
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- 239000011411 calcium sulfoaluminate cement Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000004568 cement Substances 0.000 claims abstract description 88
- 239000011575 calcium Substances 0.000 claims abstract description 45
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 43
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 42
- 239000011707 mineral Substances 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910004261 CaF 2 Inorganic materials 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 38
- 239000011812 mixed powder Substances 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000010440 gypsum Substances 0.000 claims description 11
- 229910052602 gypsum Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910001570 bauxite Inorganic materials 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 31
- 239000012071 phase Substances 0.000 abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 20
- 239000003469 silicate cement Substances 0.000 abstract description 17
- 229910052918 calcium silicate Inorganic materials 0.000 abstract description 10
- 235000012241 calcium silicate Nutrition 0.000 abstract description 9
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
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- 239000002131 composite material Substances 0.000 abstract description 3
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- 235000012054 meals Nutrition 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 24
- 238000003825 pressing Methods 0.000 description 18
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 17
- 238000005303 weighing Methods 0.000 description 17
- 238000011161 development Methods 0.000 description 15
- 238000010304 firing Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 239000011398 Portland cement Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 150000004683 dihydrates Chemical class 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000011002 quantification Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 6
- 235000019976 tricalcium silicate Nutrition 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001653 ettringite Inorganic materials 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004566 building material Substances 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
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Abstract
The application discloses an alist-belite-calcium sulfoaluminate cement clinker prepared by ion doping and a method thereof, wherein the clinker comprises the following mineral phase components in percentage by mass 3 S：30～50％，C 2 S：30～50％，C 4 A 3 $：10～20％，C 4 AF：0～5％，CaSO 4 :0 to 5 percent. The ion oxide doped in the clinker comprises metal ion oxide and nonmetal ion oxide, and is also doped with mineralizer. The cement clinker is prepared by high-temperature calcination of the mineralizer combined with the composite doping modification of the metal and the nonmetallic ions, wherein the metal ions are favorable for reducing the generation temperature of the alist, and the nonmetallic ions are favorableTo form and retain high-temperature high-activity belite, mineralizer CaF 2 The method is favorable for reducing the liquid phase forming temperature of clinker, thereby enabling the alist and the calcium sulfoaluminate to coexist in a temperature range of 1250-1350 ℃, improving the working performance of cement, improving the early strength compared with silicate cement, reducing the production cost of the silicate cement and reducing the carbon emission in the cement production process.
Description
Technical Field
The application belongs to the technical field of cement material production, and particularly relates to an alist-belite-calcium sulfoaluminate cement clinker prepared by ion doping and a method thereof.
Background
The cement industry belongs to the traditional industry with high energy consumption and high carbon emission, and the reduction of the energy consumption and the carbon emission of the cement industry is always an important problem to be solved by the cement industry. Meanwhile, cement is a key factor determining the performance of concrete as one of the main components of concrete. Nowadays, concrete is developed in the direction of high performance, low energy consumption, excellent durability and more meeting ecological requirements. In order to comply with this trend, cements must have high strength, excellent durability, and low environmental load. Therefore, how to meet the low-carbon goal of the production of conventional Portland cement is an important research in the cement field. The preparation of low-calcium high-gelation Portland cement is an epoch-making step in Portland cement production. The low-calcium high-gelation Portland cement not only needs to meet the strength required by engineering construction, but also needs to have the general property of a silicate system, so that the low-calcium high-gelation Portland cement has great engineering application significance. At the same time, the low-calcium silicate cement reduces CO in the production process 2 Is arranged in the air.
Cement systems currently under investigation and production having low carbon characteristics include sulphoaluminate cement, belite calcium sulphoaluminate cement. The sulphoaluminate cement has the characteristics of high early strength and corrosion resistance, but a large amount of high-quality bauxite is consumed in the production process, and the later strength is developed, but is inferior to that of the traditional silicate cement. The belite calcium sulfoaluminate cement reduces the use of high-quality bauxite compared with the sulphoaluminate cement, and continues the excellent characteristics of high early strength, low alkalinity, corrosion resistance and micro-expansion of the sulphoaluminate cement, but the belite calcium sulfoaluminate cement has high content of belite mineral phase, and the early strength development is fast, but the middle strength development is not kept up, so that the later strength development of the cement is influenced.
For the development of low-carbon cement at present, the carbon emission of the cement is reduced, and the content of tricalcium silicate (alite) phase in silicate cement is required to be reduced, however, the reduction of the content of tricalcium silicate phase tends to reduce the strength of the cement, while the calcium sulfoaluminate phase has the advantages of low firing temperature, high early strength and excellent erosion resistance. If the calcium sulfoaluminate phase is properly introduced into the traditional silicate cement, the defect of the silicate cement in early strength development caused by the reduction of the content of tricalcium silicate can be overcome, the energy consumption in the cement sintering process can be reduced, the carbon emission can be reduced, and the mechanical property, the working property and the durability of the cement can be enhanced. However, the theoretical calcination temperatures of the tricalcium silicate mineral phase and the calcium sulfoaluminate mineral phase are not identical, so that the tricalcium silicate mineral phase and the calcium sulfoaluminate mineral phase cannot coexist in the portland cement at the same time, and the preparation of the alite-belite-calcium sulfoaluminate cement clinker is restricted. It has been found that even if the cement clinker firing temperature is lowered by adding an appropriate amount of mineralizer, it is difficult to cause the tricalcium silicate and the calcium sulfoaluminate mineral phases to coexist in the same temperature interval, and it is difficult to fire the alite-belite-calcium sulfoaluminate cement having high performance. The firing of the alite-belite-calcium sulfoaluminate cement clinker can be realized through a secondary firing or post-firing process, but the process is complex, and the problem that the realization in the existing novel dry-method production line of silicate cement is difficult exists.
Disclosure of Invention
The application aims to: aiming at the key problem that the ore phases of the alite and the calcium sulfoaluminate are difficult to coexist, the application provides the alite-belite-calcium sulfoaluminate cement clinker prepared by ion doping and the method thereof, and the requirements of one-time calcination preparation and performance improvement based on low-carbon alite-belite-calcium sulfoaluminate cement are met.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the cement clinker comprises C in percentage by mass 3 S：30～50％，C 2 S：30～50％，C 4 A 3 $：10～20％，C 4 AF：0～5％，CaSO 4 ：0～5％。
Further, the oxide content in the clinker comprises CaO in mass percent: 50 to 65 percent of SiO 2 ：15～25％，Al 2 O 3 ：8～15％，Fe 2 O 3 ：0～5％，SO 3 : 3-8%; the doped ion oxide in the clinker comprises metal ion oxide and nonmetal ion oxide, and is also doped with mineralizer, wherein the doped ion oxide and mineralizer are not more than 6.2% of the total mass of the clinker.
Further, the metal ion oxide at least comprises MnO 2 ZnO, mgO, further include Fe 2 O 3 、K 2 O、Na 2 O, etc.; the non-metal ion oxide at least comprises B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The mineralizer is CaF 2 。
Further, the limestone saturation coefficient KH of the clinker: 0.75 to 0.78, silicon ratio SM:1.6 to 1.9, aluminum ratio IM:6.5 to 8.7, sulfur-aluminum ratio: 0.5 to 0.6.
Furthermore, the application also provides a preparation method of the cement clinker, which comprises the following steps:
(1) Grinding and fully mixing calcareous, siliceous, aluminous and sulfurous raw materials, and then adding an ionic oxide and a mineralizer for mixing to obtain raw materials; the ionic oxides comprise metal ionic oxides and nonmetal ionic oxides;
(2) Calcining the uniformly mixed raw material in the step (1) at 1250-1350 ℃ for 15-30 minutes, and then taking out and rapidly cooling to obtain the finished product.
Specifically, in the step (1), the ionic oxide includes a metal ionic oxide and a non-metal ionic oxide, and the metal ionic oxide includes at least MnO 2 ZnO, mgO, further include Fe 2 O 3 、K 2 O、Na 2 O, etc.; the non-metal ion oxide comprises at least B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The mineralizer is CaF 2 The doped ion oxide and mineralizer are not more than 6.2% of the total mass of the raw material.
Further, the ZnO is in ZnSO 4 ·H 2 O is used as a raw material to be doped; the K is 2 O is K 2 CO 3 Is added as a raw material; na (Na) 2 O is Na 2 CO 3 Is added as a raw material.
Specifically, in the step (1), the calcareous raw material is limestone, and the CaO content is more than or equal to 48wt%; the siliceous raw material is any one of sandstone, subatmospheric sand and shale, and SiO 2 The content is more than or equal to 60wt percent; the aluminum raw material is any one of bauxite and gangue, al 2 O 3 The content is more than or equal to 50wt percent; SO in the sulfur-containing raw material 3 The content is more than or equal to 40wt percent;
the raw materials comprise 60-70% of calcium raw materials, 10-15% of siliceous raw materials, 5-10% of aluminum raw materials and 5-8% of sulfur raw materials by mass percent.
Specifically, in the step (1), all raw materials are ground and fully and uniformly mixed, and the screen residue of a mixed powder with a particle size of 74 mu m is less than or equal to 5%.
Preferably, in the step (2), the temperature rising rate of calcination is 5-10 ℃/min, and the calcination is rapidly cooled in an air cooling mode after the end of calcination.
Furthermore, the application also claims an alite-belite-calcium sulfoaluminate cement, which is obtained by fully mixing the prepared clinker with gypsum with the mass of 5-14% of the clinker.
The patent of the application provides a method for solving the coexistence problem of high-temperature calcination of the phases of alite and calcium sulfoaluminate by combining metal and nonmetal ion composite doping and mineralizer modification, and is a key for ensuring the preparation of the alite-belite-calcium sulfoaluminate cement. The bulk formation temperature of the alite ore phase is above 1430 ℃, the formation temperature of the calcium sulfoaluminate phase is in the range of 1150-1250 ℃, and the calcium sulfoaluminate phase is decomposed above 1250 ℃, so that the alite ore phase and the calcium sulfoaluminate ore phase cannot coexist theoretically in the high-temperature calcination preparation of cement clinker. Mineralizers such as fluorite are usually adopted in the preparation of silicate cement calcination, so that the clinker calcination temperature can be properly reduced, but the coexistence problem of the alite and calcium sulfoaluminate phases cannot be solved. In the past researches and patents, sectional calcination or post-calcination technology is adopted to realize coexistence of the alite and calcium sulfoaluminate mineral phases in cement clinker, however, the preparation of the domestic silicate cement at present adopts novel dry cement production technology, and the sectional calcination and post-calcination technology method is difficult to realize under the current cement preparation technology conditions. Thus, the preparation of the alist-belite-calcium sulfoaluminate cement by adopting one-time continuous production process is a difficult point in the prior research!
Compared with the prior art, the application has the following beneficial effects:
(1) The application prepares the alite-belite-calcium sulfoaluminate cement clinker by high-temperature calcination of the metal and nonmetal ion composite doping modification combined mineralizer, wherein the metal ion Mn, zn, mg, fe, K, na is favorable for reducing the generation temperature of the alite, and the nonmetal ion B is favorable for forming and retaining the high-temperature high-activity belite (alpha '' H -C 2 S), mineralizer CaF 2 Is beneficial to reducing the liquid phase forming temperature of clinker, thereby leading the alist and the calcium sulfoaluminate to coexist in the temperature range of 1250-1350 ℃. The alite mineral phase (C) in the alite-belite-calcium sulfoaluminate cement clinker 3 S) content can reach 30-50%, calcium sulfoaluminate (C) 4 A 3 The content is 10% -20%, the working performance of cement is improved, the early strength is improved compared with silicate cement, the production cost of the silicate cement is reduced, and the carbon emission in the cement production process is reduced.
(2) The alist-belite-calcium sulfoaluminate cement provided by the application has the characteristic of low energy consumption. In industrial production, the calcination temperature of silicate cement is 1450 ℃, the calcination temperature of the alist-belite-calcium sulfoaluminate cement provided by the patent is 1250-1350 ℃, and the calcination temperature is reduced by 100-200 ℃ compared with that of common silicate cement. The standard coal consumption of the production of the alite-belite-calcium sulfoaluminate cement is reduced by about 10kg/t compared with that of the ordinary Portland cement, and the energy consumption is reducedThe reduced carbon emissions were about 25kg/t. Therefore, the alist-belite-calcium sulfoaluminate cement provided by the patent has lower energy consumption, and is beneficial to reducing the cement production cost and CO 2 Discharge amount.
(3) The alite-belite-sulphoaluminate cement has the mechanical property characteristics of high early strength and continuous development of later strength. The alite-belite-sulphoaluminate cement has the advantages of silicate cement and sulphoaluminate cement. The Portland cement has high alite content and moderate belite content, so that the Portland cement has moderate early strength and good later strength; the calcium sulfoaluminate in the ore phase of the sulfoaluminate cement has high content, so that the early strength is high, and the later strength is slow to develop. The alist-belite-calcium sulfoaluminate cement provided by the patent has higher alist content, moderate calcium sulfoaluminate and belite content, has the characteristics of high early strength and continuous development of later strength, and simultaneously has good shrinkage resistance and erosion resistance, and the working performance and durability of the cement are greatly improved compared with those of silicate cement.
(4) The alite-belite-calcium sulfoaluminate cement has the characteristics of low calcium and low carbon. Carbon emission reduction in the building material industry tends to reduce the carbon emission in the cement production process. Due to CaCO in the cement production process 3 Decompose to release a large amount of CO 2 About 58% of the carbon emission in the whole cement production process, thereby realizing carbon emission reduction in the cement production process and being necessary to reduce CaCO 3 Is used in the amount of (3). Compared with silicate cement, the calcium reduction amount and the carbon reduction amount of the alite-belite-calcium sulfoaluminate cement are about 8-15%, so that the carbon discharge is greatly reduced, and the low-carbon development of a cement process is promoted.
Drawings
The foregoing and/or other advantages of the application will become more apparent from the following detailed description of the application when taken in conjunction with the accompanying drawings and detailed description.
Figure 1 is the XRD pattern of the cement clinker mineral of the alist-belite-calcium sulphoaluminate of examples 1 to 5.
Figure 2 is an XRD quantitative pattern of the alist-belite-calcium sulphoaluminate cement clinker minerals of examples 1 to 5.
Fig. 3 is a lithogram of the calcium alist-belite-sulphoaluminate cement clinker of example 1.
FIG. 4 is a bar graph of compressive strength for the cements of examples 1-5 hydrated for 3 days, 7 days, and 28 days.
FIG. 5 is XRD patterns of hydration products of the cements of examples 1 to 5 for 3 days and 28 days.
Fig. 6 is an XRD pattern of the alist-belite-calcium sulfoaluminate cement clinker minerals of comparative examples 1 to 4.
Fig. 7 is an XRD quantitative pattern of the alist-belite-calcium sulfoaluminate cement clinker minerals of comparative examples 1 to 4.
FIG. 8 is a bar graph of compressive strength of cements of comparative examples 1 to 4 after hydration for 3 days and 28 days.
Detailed Description
The application will be better understood from the following examples.
In the following examples, the raw materials used are shown in table 1.
TABLE 1
The clinker oxide content (wt.%) designed in examples 1 to 5 is shown in table 2.
TABLE 2
Mechanical property detection is carried out in each example and comparative example, and the preparation steps of the cement paste sample are as follows:
(1) Weighing a proper amount of alist-belite-calcium sulfoaluminate cement, and preparing cement paste by adopting a water-cement ratio of 0.3;
(2) Stirring the cement paste in a stirrer for 3-4 minutes;
(3) Pouring the cement paste obtained by stirring into a cement standard paste 20mm x 20mm die, and compacting for 60s on a cement mortar compaction table;
(4) Scraping off superfluous cement paste on the surface of the mould, and placing the mould in a cement concrete standard curing box for curing for 24 hours;
(5) And (3) demolding the test piece, and then placing the cement paste test piece in a standard curing box with the RH of 95% and the temperature of 20 ℃ for curing to the ages of 3d, 7d and 28d respectively.
Example 1
The preparation method of the alite-belite-calcium sulfoaluminate cement in the example 1 is as follows:
(1) The oxide content in the clinker is CaO:59.4%, siO 2 ：20.1％，Al 2 O 3 ：10.9％，SO 3 :5.4 percent of calcareous, siliceous, aluminous and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are MnO 2 ：0.8％，ZnO：1.0％，MgO：0.8％，B 2 O 3 ：0.6％，CaF 2 :1.0%, weighing MnO 2 ：0.8g，ZnSO 4 ·H 2 O：2.2g，MgO：0.8g，B 2 O 3 ：0.6g，CaF 2 :1g, mixing in a mixing tank, wherein the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5%.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1300 ℃ for 30 minutes, and then rapidly cooling by adopting an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
From the XRD and quantification of clinker in FIGS. 1 and 2, it can be seen that the clinker of example 1 contains C 3 S：40.6％、C 2 S：25.9％、C 4 A 3 $：19.6％、α’ H -C 2 S:9.7%. It can also be seen in FIG. 3 that the addition of MgO, znO, mgO reduces C by the presence of the mineral of the alist and calcium sulfoaluminate 3 Firing temperature of S promotes C 3 S and C 4 A 3 Coexisting at low temperature. B (B) 2 O 3 Is added with alpha 'which can make high temperature and high activity' H -C 2 The S crystal form is preserved when cooled. Meanwhile, as shown in the compressive strength bar graph in fig. 4, the clinker strength of 3 days can reach 45.89MPa, the clinker strength of 28 days is 93.26MPa, and the clinker has higher early strength development and good later strength. The hydrated XRD pattern in FIG. 5 shows C in clinker at 28 days 4 A 3 The peak intensity was reduced relative to 3 days, and Ettringite (Ettringite) was gradually formed by hydration.
Example 2
The preparation method of the alite-belite-calcium sulfoaluminate cement in the example 2 is as follows:
(1) The oxide content in the clinker is CaO:58.9%, siO 2 ：19.9％，Al 2 O 3 ：10.8％，SO 3 :5.4 percent of calcareous, siliceous, aluminous and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are MnO 2 ：0.8％，ZnO：1.0％，MgO：0.8％，K 2 O：0.8％，B 2 O 3 ：0.6％，CaF 2 :1.0%, weighing MnO 2 ：0.8g，ZnSO 4 ·H 2 O：2.2g，MgO：0.8g，K 2 CO 3 ：1.18g，B 2 O 3 ：0.6g，CaF 2 :1g of the mixed powder is mixed in a mixing tank, the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5 percent.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1300 ℃ for 30 minutes, and then rapidly cooling by adopting an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
From the XRD and quantification of clinker in FIGS. 1 and 2, it can be seen that the clinker of example 2 contains C 3 S：41.6％、C 2 S：25.4％、C 4 A 3 $：20.1％、α’ H -C 2 S：10.1％。K 2 The addition of O can slightly increase C 3 S and C 4 A 3 The amount of minerals produced and alpha' H -C 2 The S mineral content is also slightly increased. As can be seen from the compressive strength bar graph in FIG. 4, the 3-day clinker strength can reach 47.56MPa, and the 28-day clinker strength is 95.68MPa, which is improved compared with that in example 1. FIG. 5 hydrated XRD it can be seen that, in comparison with example 1, example 2, ca (OH) for 3 days 2 The peak intensity is high and may be beneficial for strength development.
Example 3
The preparation method of the alite-belite-calcium sulfoaluminate cement in the example 3 is as follows:
(1) The oxide content in the clinker is CaO:58.8%, siO 2 ：19.8％，Al 2 O 3 ：10.8％，SO 3 :5.4 percent of calcareous, siliceous, aluminous and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are MnO 2 ：0.8％，ZnO：1.0％，MgO：1.0％，Na 2 O：0.8％，B 2 O 3 ：0.6％，CaF 2 :1.0%, weighing MnO 2 ：0.8g，ZnSO 4 ·H 2 O：2.2g，MgO：1.0g，Na 2 CO 3 ：1.37g，：B 2 O 3 ：0.6g，CaF 2 :1g of the mixed powder is mixed in a mixing tank, the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5 percent.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1300 ℃ for 30 minutes, and then rapidly cooling by adopting an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
From the XRD and quantification of clinker in FIGS. 1 and 2, it can be seen that the clinker of example 3 contains C 3 S：40.1％、C 2 S：27.6％、C 4 A 3 $：18.9％、α’ H -C 2 S：5.6％。Na 2 The addition of O increases C compared to example 1 2 S mineral content, alpha 'is reduced' H -C 2 S mineral content. From the compressive strength bar graph in FIG. 4, the early 3-day clinker strength can reach 36.65MPa, and the 28-day strength is 88.69MPa, which is reduced compared with the strength of example 1. At alpha' H -C 2 In the case of a large reduction in S minerals, the early strength development is markedly reduced. At the same time, as can be seen in the hydrated XRD of FIG. 5, there is a small portion of C in the 28-day hydrated product of example 3 4 A 3 The minerals are not hydrated, ca (OH) 2 The peak intensity is higher than in example 1, and the mineral ettringite content providing strength is relatively low and the strength is lower.
Example 4
The preparation method of the alite-belite-calcium sulfoaluminate cement in example 4 is as follows:
(1) The oxide content in the clinker is CaO:58.6%, siO 2 ：19.6％，Al 2 O 3 ：10.3％，SO 3 :5.4 percent of calcareous, siliceous, aluminous and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are MnO 2 ：0.8％，ZnO：1.0％，MgO：1.0％，Fe 2 O 3 ：0.8％，B 2 O 3 ：0.6％，CaF 2 :2.0%, weighing MnO 2 ：0.8g，ZnSO 4 ·H 2 O：2.2g，MgO：1.0g，Fe 2 O 3 ：0.8g，：B 2 O 3 ：0.6g，CaF 2 :2g of the mixed powder is mixed in a mixing tank, the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5 percent.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1280 ℃ for 30 minutes, and then rapidly cooling the calcined cake in an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
From the XRD and quantification of clinker in FIGS. 1 and 2, it can be seen that the clinker of example 4 contains C 3 S：31.4％、C 2 S：44.7％、C 4 A 3 The following steps: 15.7%. Fe in example 4 relative to example 1 2 O 3 Is mixed into clinker C 3 S and C 4 A 3 The production of minerals is unfavorable and increases C 2 S mineral formation, at the same time alpha' H -C 2 S minerals were not formed. Due to CaF 2 An increase in the amount of the catalyst, so that the firing temperature is lowered, and the decrease in the firing temperature may be related to C 3 S and C 4 A 3 The production of minerals has a major impact. As seen from the compressive strength bar graph in FIG. 4, the early 3-day clinker strength can reach 32.25MPa, and the 28-day clinker strength is 81.56MPa. Without alpha' H -C 2 S mineral, the early strength of cement is reduced more obviously. FIG. 5 hydration of Ca (OH) for 28 days in XRD 2 The content was also higher, and the strength was also lower than in example 1.
Example 5
The preparation method of the alite-belite-calcium sulfoaluminate cement in example 5 is as follows:
(1) The oxide content in the clinker is CaO:59.0%, siO 2 ：19.5％，Al 2 O 3 ：10.4％，SO 3 :5.5 percent of calcareous, siliceous, aluminous and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are MnO 2 ：1.6％，ZnO：1.0％，MgO：1.0％，Fe 2 O 3 ：0.4％，B 2 O 3 ：0.6％，CaF 2 :1.0%, weighing MnO 2 ：1.6g，ZnSO 4 ·H 2 O：2.2g，MgO：1.0g，Fe 2 O 3 ：0.4g，：B 2 O 3 ：0.6g，CaF 2 :1g of the mixed powder is mixed in a mixing tank, the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5 percent.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1320 ℃ for 15 minutes, and then rapidly cooling by adopting an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
From the XRD and quantification of clinker in FIGS. 1 and 2, it can be seen that the clinker of example 5 contains C 3 S：29.2％、C 2 S：36.0％、C 4 A 3 $：15.3％、α’ H -C 2 S:10.9%. The MnO is added in example 5 relative to example 1 2 At the same time reduce the Fe content 2 O 3 The mixing amount is increased, the calcining temperature is increased, the heat preservation time is reduced, and the C is greatly reduced 3 S and C 4 A 3 The amount of minerals produced, but also contributes to alpha' H -C 2 S mineral generation. As seen from the compressive strength bar graph in FIG. 4, the early 3 daysThe clinker strength can reach 40.51MPa, and the 28-day strength is 73.44MPa. Due to alpha' H -C 2 The presence of S mineral has significantly higher early strength than in example 4. Due to clinker C 3 S and C 4 A 3 The mineral content was low and FIG. 5 hydrates Ca (OH) for 28 days in XRD 2 The peak strengths of the cement and ettringite are low, the amount of minerals which are produced by hydration of the cement and provide strength is small, and the later strength is also reduced.
The clinker oxide content (wt.%) designed in comparative examples 1 to 4 is shown in table 3.
TABLE 3 Table 3
Comparative example 1
The preparation method of the alite-belite-calcium sulfoaluminate cement in comparative example 1 is as follows:
(1) The oxide content in the clinker is CaO:60.6%, siO 2 ：20.5％，Al 2 O 3 ：11.5％，SO 3 :5.4 percent of calcareous, siliceous, aluminous and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are MnO 2 ：1.0％，CaF 2 :1.0%, weighing MnO 2 ：1.0g，CaF 2 :1g, mixing in a mixing tank, wherein the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5%.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1300 ℃ for 30 minutes, and then rapidly cooling by adopting an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
From the XRD and quantification of clinker in FIGS. 6 and 7, it can be seen that the clinker of comparative example 1 contains C 3 S：21.5％、C 2 S：57.9％、C 4 A 3 $：7.3％、α’ H -C 2 S：0.6％、C 4 AF:5.6%. Singly mix MnO 2 For C in clinker 3 S and C 4 A 3 Firing does not help. As can be seen from the compressive strength of FIG. 8, due to alpha' H -C 2 S and C 4 A 3 The mineral content is too small, and the 3-day strength of the cement sample is only 13.5MPa. Because of containing 21.5% of C 3 S and 57.9% C 2 S, the 28-day strength of the cement sample is greatly improved compared with that of the cement sample in 3 days, but the cement sample is only 46.28MPa.
Comparative example 2
The preparation method of the alite-belite-calcium sulfoaluminate cement in comparative example 2 is as follows:
(1) The oxide content in the clinker is CaO:60.6%, siO 2 ：20.5％，Al 2 O 3 ：11.5％，SO 3 :5.4 percent of calcareous, siliceous, aluminum and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are ZnO:1.0%, caF 2 :1.0%, weighing ZnO:1.0g, caF 2 :1g, mixing in a mixing tank, wherein the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5%.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1300 ℃ for 30 minutes, and then rapidly cooling by adopting an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
The following conclusions were drawn after a series of tests on samples of the cement paste prepared according to the embodiments:
from the XRD and quantification of clinker in FIGS. 6 and 7, it can be seen that the clinker of comparative example 2 contains C 3 S：27.6％、C 2 S：41.9％、C 4 A 3 $：15.7％、C 4 AF:9.9%. In comparison with comparative example 1, single ZnO doped with C in clinker 3 S and C 4 A 3 Firing is helpful, but not alpha' H -C 2 S mineral generation. As can be seen from the compressive strength of FIG. 8, the cement sample had a 3-day strength of 25.69MPa. The strength of the product is improved in 28 days compared with that of the comparative example 1, and can reach 55.69MPa.
Comparative example 3
The preparation method of the alite-belite-calcium sulfoaluminate cement in comparative example 3 is as follows:
(1) The oxide content in the clinker is CaO:60.6%, siO 2 ：20.5％，Al 2 O 3 ：11.5％，SO 3 :5.4 percent of calcareous, siliceous, aluminum and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are MgO:1.0%, caF 2 :1.0%, mgO is weighed: 1.0g, caF 2 :1g, mixing in a mixing tank, wherein the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5%.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1300 ℃ for 30 minutes, and then rapidly cooling by adopting an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
The following conclusions were drawn after a series of tests on samples of the cement paste prepared according to the embodiments:
from the XRD and quantification of clinker in FIGS. 6 and 7, it can be seen that the clinker of comparative example 3 contains C 3 S：16.3％、C 2 S：55.0％、C 4 A 3 $：10.1％、α’ H -C 2 S：6.2％、C 4 AF:6.1%. Single MgO doped C in clinker 3 S and C 4 A 3 Firing does not help, and alpha 'is increased compared to comparative example 1' H -C 2 S, S. As can be seen from the compressive strength of FIG. 8, due to alpha' H -C 2 S mineral was present, and the 3-day strength of the cement sample was slightly improved by 20.35MPa compared to comparative example 1 but due to C 3 S and C 4 A 3 The cement sample had a low mineral content and a 28-day strength comparable to that of comparative example 1, only 42.36MPa.
Comparative example 4
The preparation method of the alite-belite-calcium sulfoaluminate cement in comparative example 4 is as follows:
(1) The oxide content in the clinker is CaO:60.6%, siO 2 ：20.5％，Al 2 O 3 ：11.5％，SO 3 :5.4 percent of calcareous, siliceous, aluminous and sulfur-containing materials are weighed, and the ions added according to the oxide content in the clinker are B 2 O 3 ：1.0％，CaF 2 :1.0 percent, weight B 2 O 3 ：1.0g，CaF 2 :1g, mixing in a mixing tank, wherein the particle size of the mixed powder is about 74 mu m, and the screen residue is less than or equal to 5%.
(2) The method for pressing the raw meal into the raw cake comprises the following steps: weighing a proper amount of raw meal, mixing with deionized water accounting for 10% of the raw meal in percentage by mass, pressing into a raw meal cake with 60mm by 5mm square by using a press machine, and drying in a blast drier at 100 ℃ for 8 hours.
(3) Calcining the dried raw cake at 1300 ℃ for 30 minutes, and then rapidly cooling by adopting an air cooling mode to obtain the alite-belite-calcium sulfoaluminate clinker.
(4) Mixing the clinker with 10% by mass of dihydrate gypsum to obtain mixed powder, grinding the mixed powder to a particle size of about 74 mu m through a disc type vibration mill, and obtaining the alite-belite-calcium sulfoaluminate cement with a screen residue of less than or equal to 5%.
The following conclusions were drawn after a series of tests on samples of the cement paste prepared according to the embodiments:
from the XRD and quantification of clinker in FIGS. 6 and 7, it can be seen that the clinker of comparative example 4 contains C 3 S：22.6％、C 2 S：44.9％、C 4 A 3 $：13.7％、α’ H -C 2 S：9.1％、C 4 AF:4.7%. Singly mix B 2 O 3 A small amount of C in clinker 3 S and C 4 A 3 The mineral content is mainly increased by alpha' H -C 2 S mineral content. As can be seen from the compressive strength of FIG. 8, due to alpha' H -C 2 S and C 4 A 3 The improvement of mineral content, the 3-day strength of the cement sample is higher than that of the cement sample in comparative example 1, and the strength can reach 32.25MPa. Meanwhile, the 28-day strength is the highest of all the single-doped comparative examples, and can reach 65.63MPa.
It can be seen from all the above examples that although a single doping of part of the ions can raise C in the clinker 3 S、C 4 A 3 $ and alpha' H -C 2 The S mineral content, however, is very different in effect with respect to the ion remixing. At the same time, it can be seen from the compressive strength results of the cement samples that even a single admixture of B is relatively most useful 2 O 3 The compressive strength of the alloy in 28 days still cannot catch up with the compressive strength of the example 5 with relatively minimal effect after re-doping. Therefore, experiments prove that the synergistic effect exists between different ions involved in the experiments through the double doping, the effect is far greater than that of single doping, and the synergistic effect generated by the double doping among different ions plays an important role in successfully preparing the alite-belite-calcium sulfoaluminate cement clinker.
In addition, the alite-belite-sulphoaluminate cement has the mechanical property characteristic of high early strength and continuous development of later strength. The alite-belite-sulphoaluminate cement has the advantages of silicate cement and sulphoaluminate cement. The mineral phase content in the Portland cement is shown in Table 4, the alite content is high, and the belite content is moderate, so that the early strength is moderate, and the later strength is good; the mineral phase content of the sulphoaluminate cement is shown in table 4, wherein the calcium sulphoaluminate is high in content, so that the early strength is high, and the later strength development is slow. The calcium reduction amount and the carbon reduction amount of the alite-belite-calcium sulfoaluminate cement are about 8% -15% (shown in table 4), so that the carbon discharge is greatly reduced, and the low-carbon development of a cement process is promoted.
TABLE 4 calcium and carbon reduction for various cements (%)
* With CaCO only in the clinker preparation process per ton 3 Decomposing CO calculated 2 Discharge amount.
In conclusion, the alist-belite-calcium sulfoaluminate cement provided by the patent has the characteristics of low carbon, low energy consumption and high performance, reduces environmental pollution, provides an important direction for the low carbon development of the cement industry, promotes the transformation of the building material industry, and brings considerable economic and social benefits to enterprises and society.
The application provides an alemter-belite-calcium sulfoaluminate cement clinker prepared by ion doping, a method thought and a method, and a method for realizing the technical scheme, wherein the method and the method are a plurality of methods, the above is only a preferred embodiment of the application, and it is pointed out that a plurality of improvements and modifications can be made by one of ordinary skill in the art without departing from the principle of the application, and the improvements and modifications are also considered as the protection scope of the application. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (10)
1. An alist-belite-calcium sulphoaluminate cement clinker prepared by ion doping is characterized in that the clinker comprises the following mineral phase components in percentage by mass 3 S：30～50％，C 2 S：30～50％，C 4 A 3 $：10～20％，C 4 AF：0～5％，CaSO 4 ：0～5％。
2. The ion doped prepared alite-belite-calcium sulfoaluminate cement clinker according to claim 1, wherein the oxide content in the clinker comprises CaO in mass percent: 50 to 65 percent of SiO 2 ：15～25％，Al 2 O 3 ：8～15％，Fe 2 O 3 ：0～5％，SO 3 : 3-8%; the doped ion oxide in the clinker comprises metal ion oxide and nonmetal ion oxide, and is also doped with mineralizer, wherein the doped ion oxide and mineralizer are not more than 6.2% of the total mass of the clinker.
3. The ion doped cement clinker of alite-belite-calcium sulfoaluminate prepared in accordance with claim 2, wherein said metal ion oxide comprises at least MnO 2 ZnO, mgO; the non-metal ion oxide at least comprises B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The mineralizer is CaF 2 。
4. The ion doped prepared alite-belite-calcium sulfoaluminate cement clinker according to claim 1 or 2, characterized by the limestone saturation coefficient KH of the clinker: 0.75 to 0.78, silicon ratio SM:1.6 to 1.9, aluminum ratio IM:6.5 to 8.7, sulfur-aluminum ratio: 0.5 to 0.6.
5. The method for preparing cement clinker as claimed in claim 1, comprising the steps of:
(1) Grinding and fully mixing calcareous, siliceous, aluminous and sulfurous raw materials, and then adding an ionic oxide and a mineralizer for mixing to obtain raw materials; the ionic oxides comprise metal ionic oxides and nonmetal ionic oxides;
(2) Calcining the uniformly mixed raw material in the step (1) at 1250-1350 ℃ for 15-30 minutes, and then taking out and rapidly cooling to obtain the finished product.
6. Cement clinker according to claim 5The preparation method is characterized in that in the step (1), the ionic oxide comprises metal ionic oxide and nonmetal ionic oxide, and the metal ionic oxide at least comprises MnO 2 ZnO, mgO, non-metal ion oxide at least comprises B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The mineralizer is CaF 2 The doped ion oxide and mineralizer are not more than 6.2% of the total mass of the raw material.
7. The method for producing cement clinker according to claim 5, wherein in the step (1), the calcareous raw material is limestone, and the CaO content is not less than 48wt%; the siliceous raw material is any one of sandstone, subatmospheric sand and shale, and SiO 2 The content is more than or equal to 60wt percent; the aluminum raw material is any one of bauxite and gangue, al 2 O 3 The content is more than or equal to 50wt percent; SO in the sulfur-containing raw material 3 The content is more than or equal to 40wt percent;
the raw materials comprise 60-70% of calcium raw materials, 10-15% of siliceous raw materials, 5-10% of aluminum raw materials and 5-8% of sulfur raw materials by mass percent.
8. The method of producing cement clinker as claimed in claim 5, wherein in step (1), all the raw materials are ground and thoroughly mixed to be uniform, and the screen residue of the mixed powder having a particle size of 74 μm is not more than 5%.
9. The method of producing cement clinker according to claim 5, wherein in step (2), the temperature rising rate of calcination is 5 to 10 ℃/min, and the rapid cooling is performed by air cooling after the completion of calcination.
10. An alite-belite-calcium sulfoaluminate cement, which is characterized in that the clinker according to claim 1 is fully mixed with gypsum with the mass of 5-14% of clinker.
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