CN117361913A - Calcium silicate-calcium sulfoaluminate cement clinker and preparation method thereof - Google Patents
Calcium silicate-calcium sulfoaluminate cement clinker and preparation method thereof Download PDFInfo
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- 239000011575 calcium Substances 0.000 title claims abstract description 118
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 118
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000011411 calcium sulfoaluminate cement Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title description 11
- 239000004568 cement Substances 0.000 claims abstract description 94
- 239000002994 raw material Substances 0.000 claims abstract description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 27
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 27
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 27
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 26
- 239000010440 gypsum Substances 0.000 claims abstract description 26
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 23
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 235000019738 Limestone Nutrition 0.000 claims abstract description 14
- 239000010881 fly ash Substances 0.000 claims abstract description 14
- 239000006028 limestone Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 12
- 229910052925 anhydrite Inorganic materials 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 18
- 239000011707 mineral Substances 0.000 description 18
- 238000006703 hydration reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000036571 hydration Effects 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000011002 quantification Methods 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- AGWMJKGGLUJAPB-UHFFFAOYSA-N aluminum;dicalcium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Ca+2].[Ca+2].[Fe+3] AGWMJKGGLUJAPB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- -1 silicon ions Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052600 sulfate mineral Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
-
- 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
-
- 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
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
- C04B7/425—Acids or salts thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to the field of building materials, and discloses a calcium sulfosilicate-calcium sulfoaluminate cement clinker, which comprises the following components: 35-60 wt.% of calcium sulfosilicate, 20-45 wt.% of calcium sulfoaluminate, 0-5 wt.% of belite, 2-10 wt.% of high-temperature anhydrite and 2-10 wt.% of iron phase, wherein the mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate in the cement clinker is 0.78-3; the cement raw material is prepared by mixing and grinding 52.49 to 65.67 parts by mass of limestone, 35.92 to 43.62 parts by mass of gypsum, 8.85 to 35.63 parts by mass of bauxite, 0.22 to 25.69 parts by mass of fly ash, 0 to 1 part by mass of calcium fluoride and the like according to the mass ratio; and (3) placing the cement raw material into a high-temperature furnace for calcination, and rapidly cooling to room temperature after the calcination is completed to obtain the cement clinker. The cement clinker provided by the invention can effectively reduce the production energy consumption and effectively improve the later mechanical properties of the cement clinker.
Description
Technical Field
The invention relates to the field of building materials, in particular to calcium sulfosilicate-calcium sulfoaluminate cement clinker and a preparation method thereof.
Background
The sulphoaluminate cement has the excellent characteristics of quick hardening, early strength, corrosion resistance, freezing resistance and the like, and is sintered at the temperature and CO 2 Emissions are all lower than conventional portland cement and are of great concern.
The sulphoaluminate cement clinker is prepared by taking limestone, bauxite and gypsum as raw materials and calcining the raw materials at low temperature, and has higher quality requirements on aluminum raw materials, and generally adopts high-grade bauxite with higher aluminum content and lower silicon content as aluminum materials, wherein main minerals are calcium sulphoaluminate and dicalcium silicate; calcium sulfosilicate has been regarded as an inert mineral and its presence is avoided during the production of sulfoaluminate cement clinker, but recent studies have found that calcium sulfosilicate has a certain hydration potential which, in the presence of calcium sulfoaluminate, is activated and higher than belite. Belite, dicalcium silicate, is the main mineral of silicate cement clinker and sulphoaluminate cement clinker, and has slower hydration speed and lower hydration heat release.
Cement clinker system using calcium sulfosilicate and calcium sulfoaluminate as dominant minerals, not only CO 2 The discharge is lower, the quality requirement on bauxite can be reduced, and the hydration of calcium sulfosilicate can improve the later mechanical property of cement. Therefore, the calcium silicate-calcium sulfoaluminate cement clinker system has wide application prospect.
However, the mass formation temperature of calcium sulfoaluminate is 1200-1300 ℃, the mass formation temperature of calcium sulfosilicate is 1100-1200 ℃, the mass formation temperatures of two minerals are inconsistent and difficult to coexist, and although the hydration product aluminum gel of the calcium sulfoaluminate can excite the hydration activity of the calcium sulfosilicate, the excitation effect is relatively poorer than that of other aluminum-containing minerals (tricalcium aluminate, dodecacalcium heptaluminate and calcium aluminate), mainly due to the co-sulfate ion effect of the two minerals of the calcium sulfoaluminate and the calcium sulfosilicate. When the calcium sulfosilicate and the belite exist in the cement clinker at the same time and the content of the calcium sulfosilicate is higher than that of the belite, the dissolution of the calcium sulfosilicate in the hydration process enables silicon ions in the pore solution to reach saturation, so that the belite hydration is inhibited, and the later strength development of the cement clinker is affected.
Disclosure of Invention
The invention aims to provide a calcium fluosilicate-calcium fluoaluminate cement clinker and a preparation method thereof, so as to optimize the mineral composition of the calcium fluosilicate-calcium fluoaluminate cement clinker, enable the calcium fluosilicate-calcium fluoaluminate cement clinker to be easy to calcine and improve the later mechanical property of the cement clinker.
In order to achieve the above purpose, the invention adopts the following technical scheme: a calcium aluminosilicate-calcium sulfoaluminate cement clinker comprising the following components: 35-60 wt.% of calcium sulfosilicate, 20-45 wt.% of calcium sulfoaluminate, 0-5 wt.% of belite, 2-10 wt.% of high-temperature anhydrite and 2-10 wt.% of iron phase, wherein the mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate in the cement clinker is 0.78-3.
The principle of the scheme is as follows: the mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate in the clinker is regulated so that the sulfate radical content generated by the dissolution of the calcium sulfosilicate is larger than that generated by the dissolution of the calcium sulfoaluminate, thereby weakening the co-sulfate ion effect brought by the calcium sulfoaluminate and improving the hydration activity of the calcium sulfosilicate; the high-temperature anhydrite is sulfate mineral generated in the process of calcining clinker at high temperature, and by regulating and controlling a small amount of high-temperature anhydrite in the clinker, calcium silicate is fully formed, and the positive effect of the calcium silicate on the later strength of the cement clinker is exerted after the belite is replaced by the calcium silicate; the iron phase is a generic term referring to iron-containing materials such as tetra calcium aluminoferrite, etc., and the cement clinker contains a small amount of iron phase, which can improve the erosion resistance of the cement and assist in the stable formation of calcium sulfoaluminate.
Further, the iron phase is C 2 F、C 4 One or two of AF. The inclusion of a small amount of iron phase in the clinker can improve the erosion resistance of the cement and aid in the stable formation of calcium sulfoaluminate.
Further, the invention also provides a preparation method of the calcium silicate-calcium sulfoaluminate cement clinker, which comprises the following steps:
s1, mixing and grinding the cement clinker raw materials according to the mass ratio to obtain cement raw materials;
and S2, placing the cement raw material obtained in the step S1 into a high-temperature furnace for calcination, and rapidly cooling to room temperature after the calcination is completed to obtain the cement clinker.
The cement clinker is obtained by grinding the raw materials of the cement clinker to obtain cement raw materials, and calcining the raw materials at high temperature.
Further, the raw materials of the cement clinker comprise the following components: 52.49 to 65.67 parts by mass of limestone, 35.92 to 43.62 parts by mass of gypsum, 8.85 to 35.63 parts by mass of bauxite, 0.22 to 25.69 parts by mass of fly ash and 0 to 1 part by mass of calcium fluoride, wherein the bauxite contains Al 2 O 3 The content is 55 to 70wt.%.
The calcium fluoride is used as mineralizer, so that the combustibility of raw materials can be improved, the absorption of CaO is facilitated, and the stable formation and coexistence of calcium sulfosilicate and calcium sulfoaluminate at low temperature are promoted; meanwhile, by adding excessive gypsum into the raw material, a small amount of high-temperature anhydrite exists in the cement clinker, so that the full formation of calcium sulfosilicate and calcium sulfoaluminate is ensured; meanwhile, a small amount of high-temperature anhydrite can generate hydration reaction with calcium sulfoaluminate, so that the early strength of cement clinker can be improved.
To facilitate the definition of Al in bauxite 2 O 3 Content of Al in bauxite 2 O 3 The content being further defined by weight percentages, e.g. Al in bauxite 2 O 3 The content is 55-70 wt%, bauxite in the raw material of cement clinker is 10 parts by mass, and Al in the raw material of cement clinker is calculated simply 2 O 3 5.5 to 7.7 parts by mass; the difference in the amount of bauxite directly results in Al 2 O 3 The weight parts are changed with the change, the bauxite takes other parts, and according to the weight percentage range, the Al can be obtained without doubt 2 O 3 Parts by weight.
Where the description hereinafter includes similar expressions, reference is made to Al in bauxite 2 O 3 The content is estimated.
In step S1, the raw materials of the cement clinker are mixed and ground, and then the raw materials are screened by a 150-200 mesh screen. The ground raw materials are screened by using a 150-200 mesh sieve, so that the influence of the large-particle raw materials which are not completely ground on the subsequent calcination process is prevented.
Further, in the step S2, the cement raw material is pressed into cakes or balls before calcination, and then calcined in a high temperature furnace at 1100-1150 ℃ for 30-60 min. By using a lower temperature than conventional calcination temperatures for calcination, calcium sulfosilicate decomposition can be avoided while promoting the adequate formation of calcium sulfosilicate and calcium sulfoaluminate minerals, while calcium sulfoaluminate formed below 1200 ℃ is more active, contributing to the improvement of early strength of cement clinker.
Further, in step S2, the rapid cooling mode adopts air blast cooling. The method of using blast cooling allows to increase the cooling rate of the clinker while keeping the clinker dry.
Furthermore, natural gypsum is added into the cement clinker, and the added part of the natural gypsum accounts for 0-15 parts of the total amount of the cement clinker and the natural gypsum after being mixed. The clinker and the natural gypsum are mixed to prepare the finished cement for building and other purposes.
The advantage of this scheme is:
1. according to the invention, most of the belite is converted into calcium sulfosilicate, the mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate in the clinker is regulated and controlled, and meanwhile, a small amount of high-temperature anhydrite is reserved in the clinker, so that the hydration activities of the calcium sulfoaluminate and the calcium sulfosilicate are fully exerted, and the early strength and the later strength of the cement clinker are improved.
2. The invention uses calcium fluoride as mineralizer, improves the combustibility of cement raw materials, and promotes the stable formation and coexistence of calcium sulfosilicate and calcium sulfoaluminate at low temperature.
3. The invention uses low-grade bauxite and fly ash as aluminum raw materials, can effectively reduce the quality requirement on bauxite, and simultaneously realizes the resource utilization of aluminum-containing solid waste.
4. The calcination temperature of the calcium sulphosilicate-calcium sulphoaluminate cement clinker is about 150-250 ℃ lower than that of the sulphoaluminate cement clinker, the production energy consumption can be effectively reduced, and the CO in the clinker preparation process is reduced 2 The discharge rate is low and the amount of the liquid in the liquid tank is low,the advantage of low carbon is remarkable.
Drawings
FIG. 1 is an XRD pattern of cement clinker prepared in example 1;
FIG. 2 is an XRD pattern of cement clinker prepared in example 2;
FIG. 3 is an XRD pattern of cement clinker prepared in example 3;
FIG. 4 is an XRD pattern of cement clinker prepared in comparative example 1;
FIG. 5 is an XRD pattern of cement clinker prepared in comparative example 2;
fig. 6 shows the compressive strength of the slurries of cement clinker prepared in examples 1 to 3 and comparative examples 1 to 2 at different ages.
Detailed Description
The following is a further detailed description of the embodiments:
in the following examples, the chemical composition (wt.%) of the starting materials is shown in table 1.
| Raw materials | CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | SO 3 | Loss on ignition |
| Limestone powder | 55.58 | 2.25 | 0.91 | 0.44 | 0.83 | 0.31 | 39.00 |
| Bauxite | 1.52 | 25.54 | 66.16 | 1.18 | 0.65 | 0.25 | 0.70 |
| Fly ash | 8.01 | 44.99 | 24.82 | 11.49 | 1.40 | 1.23 | 2.00 |
| Gypsum plaster | 35.88 | 0.51 | 0.20 | 0.12 | 0.65 | 42.43 | 19.50 |
TABLE 1
Example 1:
the raw materials of the calcium silicate-calcium sulfoaluminate cement clinker of this example were 52.49 parts by mass of limestone, 41.52 parts by mass of gypsum, 35.63 parts by mass of bauxite, 0.22 part by mass of fly ash, and 1.00 parts by mass of calcium fluoride.
The specific preparation method comprises the following steps: the limestone, bauxite, fly ash and gypsum are baked for 24 hours at 105 ℃, then mixed according to the mass ratio, and ground by a ball mill and sieved by a 200-mesh sieve, thus obtaining the cement raw material. Adding 10wt.% of water into cement raw material, pressing into cake in a mould, drying at 105 ℃, placing the raw material cake in a high-temperature furnace, calcining at 1150 ℃ for 30min, taking out, and rapidly cooling to obtain cement clinker. The mineral composition of the cement clinker, analyzed by Rietveld quantification, was 34.89wt.% calcium sulfosilicate, 44.62wt.% calcium sulfoaluminate, 5.34wt.% calcium aluminoferrite (iron phase), 5.25wt.% dicalcium silicate (belite), 9.90wt.% calcium sulfate (gypsum). The mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate in the cement clinker is 0.78.
Example 2:
the raw materials of the calcium sulfosilicate-calcium sulfoaluminate cement clinker of this example were 60.64 parts by mass of limestone, 43.62 parts by mass of gypsum, 8.85 parts by mass of bauxite, 25.28 parts by mass of fly ash, and 0.60 parts by mass of calcium fluoride.
The specific preparation method comprises the following steps: the limestone, bauxite, fly ash and gypsum are baked for 24 hours at 105 ℃, then mixed according to the mass ratio, and ground by a ball mill and sieved by a 150-mesh sieve, thus obtaining the cement raw material. Adding 10wt.% of water into cement raw material, pressing into cake in a mould, drying at 105 ℃, placing the raw material cake in a high-temperature furnace, calcining at 1150 ℃ for 45min, taking out, and rapidly cooling to obtain cement clinker. The mineral composition of the cement clinker, analyzed by Rietveld quantification, was 59.88wt.% calcium sulfosilicate, 21.24wt.% calcium sulfoaluminate, 9.56wt.% calcium aluminoferrite (iron phase), 0.63wt.% dicalcium silicate (belite), 8.69wt.% calcium sulfate (gypsum). The mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate in the cement clinker is 2.82.
Example 3:
the raw materials of the calcium sulfosilicate-calcium sulfoaluminate cement clinker of this example were 65.67 parts by mass of limestone, 35.92 parts by mass of gypsum, 14.50 parts by mass of bauxite, 25.69 parts by mass of fly ash, and 0.30 parts by mass of calcium fluoride.
The specific preparation method comprises the following steps: the limestone, bauxite, fly ash and gypsum are baked for 24 hours at 105 ℃, then mixed according to the mass proportion, and ground by a ball mill and sieved by a 180-mesh sieve, thus obtaining the cement raw material. Adding 10wt.% of water into cement raw material, pressing into cake in a mould, drying at 105 ℃, placing the raw material cake in a high-temperature furnace, calcining at 1150 ℃ for 60min, taking out and rapidly cooling after completion to obtain cement clinker. The mineral composition of the cement clinker was 59.14wt.% calcium sulfosilicate, 31.35wt.% calcium sulfoaluminate, 2.54wt.% calcium aluminoferrite (iron phase), 4.87wt.% dicalcium silicate (belite) and 2.10wt.% calcium sulfate (gypsum) as analyzed by Rietveld quantification. The mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate in the cement clinker is 1.89.
Comparative example 1:
the raw materials of the belite-calcium sulfoaluminate cement clinker of the comparative example are 73.54 parts by mass of limestone, 24.68 parts by mass of gypsum, 22.87 parts by mass of bauxite, 18.22 parts by mass of fly ash and 0.5 part by mass of calcium fluoride.
The specific preparation method comprises the following steps: the limestone, bauxite, fly ash and gypsum are baked for 24 hours at 105 ℃, then mixed according to the mass ratio, and ground by a ball mill and sieved by a 200-mesh sieve, thus obtaining the cement raw material. Adding 10wt.% of water into cement raw material, pressing into cake in a mould, drying at 105 ℃, placing the raw material cake in a high-temperature furnace, calcining at 1250 ℃ for 30min, taking out, and rapidly cooling to obtain cement clinker. The mineral composition of the cement clinker was belite 44.65wt.%, calcium sulfoaluminate 37.86wt.%, calcium aluminoferrite 6.25wt.% (iron phase), calcium sulfate 11.24wt.% (gypsum) as analyzed by Rietveld quantification.
Comparative example 2:
the raw materials of the calcium silicate-calcium sulfoaluminate cement clinker of the comparative example were 52.49 parts by mass of limestone, 41.52 parts by mass of gypsum, 35.63 parts by mass of bauxite, and 0.22 part by mass of fly ash.
The specific preparation method is the same as in example 1. The mineral composition of the cement clinker, analyzed by Rietveld quantitative analysis, was 28.57wt.% calcium sulfosilicate, 42.09wt.% calcium sulfoaluminate, 5.12wt.% calcium aluminoferrite (iron phase), 13.24wt.% dicalcium silicate (belite), 10.98wt.% calcium sulfate (gypsum). The mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate in the cement clinker is 0.68.
The cement clinker obtained by calcining examples 1 to 3 and comparative examples 1 to 2 was put in a ball mill and ground to 200 mesh sieve, then XRD test was performed at a scanning speed of 5 DEG/min and a step length of 0.01 DEG, and the results are shown in FIGS. 1 to 5.
As can be seen from fig. 1 to 3, the cement clinker of examples 1 to 3 does not have diffraction peaks of free calcium oxide, indicating that the clinker is easily burned. The high diffraction peak intensity of calcium sulfosilicate and calcium sulfoaluminate in the clinker indicates that the two minerals are well formed, and the calcium sulfoaluminate exists in two crystal forms. Small amounts of belite and high temperature anhydrite are also present in the clinker, indicating that calcium sulfosilicate and calcium sulfoaluminate are formed relatively well. From the result of Rietveld quantitative analysis, cement clinker meeting the design requirement of mineral composition can be burned at a time at 1100-1150 ℃ by adjusting the proportion of raw materials.
As can be seen from fig. 4, the calcination temperature used in comparative example 1 was 1250 ℃, and the minerals in the cement clinker were calcium sulfoaluminate, belite, high temperature anhydrite and iron phases, and diffraction peaks of calcium sulfosilicate were not seen, so that the calcination temperature of the calcium sulfosilicate-calcium sulfoaluminate cement clinker was not preferably more than 1200 ℃. The raw material composition of comparative example 2 was not blended with calcium fluoride, and the other raw materials and proportions were the same as in example 1.
From the results of fig. 5 and quantitative analysis, the mineral species in the cement clinker were unchanged, but the formation of calcium sulfosilicate and calcium sulfoaluminate was significantly reduced, indicating that calcium sulfosilicate was difficult to sufficiently form without calcium fluoride addition.
The cement clinker obtained by calcining examples 1 to 3 and comparative examples 1 to 2 was ground to a powder of 200 mesh, and then subjected to a water curing under a curing condition of 20℃at a water cement ratio of 0.4, and the compressive strength was measured, and the strength results are shown in FIG. 6.
As can be seen from fig. 6, the early strength of the calcium silicate-calcium sulfoaluminate cement clinker in example 1 is developed rapidly, and the 1d strength can reach about 42 MPa; along with the increase of the hydration age, the strength of the cement clinker in the later stage of hydration is not inverted and shows a continuous increase trend, the strength of 28d can reach 63MPa, and the hydration of calcium sulfosilicate promotes the increase of the strength of the clinker in the later stage; the post strength of the calcium sulfosilicate-calcium sulfoaluminate cement clinker in examples 2 and 3 steadily increased. The greater magnitude of the increase in the post strength of the calcium aluminosilicate-calcium sulfoaluminate cement clinker compared to the belite-calcium sulfoaluminate cement clinker of comparative example 1, indicates that the contribution of calcium sulfosilicate to the mid-post strength of cement is greater than belite. The higher strength of the cement clinker of example 1 at each age compared to the cement clinker of comparative example 2 demonstrates the promoting effect of calcium fluoride on calcium sulfosilicate formation, which is beneficial to improving cement clinker strength.
The foregoing is merely exemplary of the present invention, and specific technical solutions and/or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present invention, and these should also be regarded as the protection scope of the present invention, which does not affect the effect of the implementation of the present invention and the practical applicability of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (8)
1. A calcium aluminosilicate-calcium sulfoaluminate cement clinker, characterized in that said cement clinker comprises the following components: 35-60 wt.% of calcium sulfosilicate, 20-45 wt.% of calcium sulfoaluminate, 0-5 wt.% of belite, 2-10 wt.% of high-temperature anhydrite and 2-10 wt.% of iron phase, wherein the mass ratio of the calcium sulfosilicate to the calcium sulfoaluminate is 0.78-3.
2. The calcium sulfosilicate-calcium sulfoaluminate cement clinker according to claim 1, wherein: the iron phase is C 2 F and C 4 One or two of AF.
3. A method for preparing the calcium sulfosilicate-calcium sulfoaluminate cement clinker according to claim 1 or 2, comprising the steps of:
s1, mixing and grinding raw materials of the cement clinker according to mass proportion to obtain cement raw materials;
and S2, placing the cement raw material obtained in the step S1 into a high-temperature furnace for calcination, and rapidly cooling to room temperature after the calcination is completed to obtain the cement clinker.
4. A method for preparing a calcium sulfosilicate-calcium sulfoaluminate cement clinker according to claim 3, wherein: the raw materials of the cement clinker comprise the following components: 52.49 to 65.67 parts by mass of limestone, 35.92 to 43.62 parts by mass of gypsum, 8.85 to 35.63 parts by mass of bauxite, 0.22 to 25.69 parts by mass of fly ash and 0 to 1 part by mass of calcium fluoride, wherein the bauxite contains Al 2 O 3 The content is 55 to 70wt.%.
5. The method for preparing the calcium sulfosilicate-calcium sulfoaluminate cement clinker according to claim 4, wherein the method comprises the following steps: in the step S1, the raw materials of each cement clinker are mixed and ground, and then the raw materials are screened by a 150-200 mesh screen.
6. The method for preparing the calcium sulfosilicate-calcium sulfoaluminate cement clinker according to claim 5, wherein the method comprises the following steps: in the step S2, the cement raw material is pressed into cakes or balls before calcination, and then calcined in a high-temperature furnace at 1100-1150 ℃ for 30-60 min.
7. The method for preparing the calcium sulfosilicate-calcium sulfoaluminate cement clinker according to claim 6, wherein the method comprises the following steps: in step S2, the rapid cooling mode adopts air blast cooling.
8. A calcium sulfosilicate-calcium sulfoaluminate cement clinker according to claim 1 or 2, characterized in that: natural gypsum is also added into the cement clinker, and the added part of the natural gypsum accounts for 0-15 parts of the total amount of the cement clinker and the natural gypsum after being mixed.
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