CN117567054A - Slag sulphoaluminate cement and production method thereof - Google Patents
Slag sulphoaluminate cement and production method thereof Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 105
- 239000004568 cement Substances 0.000 title claims abstract description 102
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 103
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 100
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 42
- 239000011707 mineral Substances 0.000 claims abstract description 42
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 36
- 229910052925 anhydrite Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 25
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 19
- 239000010440 gypsum Substances 0.000 claims abstract description 19
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 17
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 17
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 8
- 239000004571 lime Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 6
- SQMWSBKSHWARHU-SDBHATRESA-N n6-cyclopentyladenosine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C2=NC=NC(NC3CCCC3)=C2N=C1 SQMWSBKSHWARHU-SDBHATRESA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 238000006703 hydration reaction Methods 0.000 description 15
- 230000036571 hydration Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011411 calcium sulfoaluminate cement Substances 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 229910001653 ettringite Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-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
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 210000004127 vitreous body Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses slag sulphoaluminate cement and a production method thereof, wherein the slag sulphoaluminate cement comprises 4-12% of calcium sulphoaluminate-calcium sulphosilicate cement clinker; 65-85% of granulated blast furnace slag or granulated blast furnace slag powder; 8-25% of anhydrite, wherein the mineral composition of the calcium sulfoaluminate-calcium sulfosilicate cement clinker meets the following conditions: 20-40 wt.% of anhydrous calcium sulfoaluminate, 30-55 wt wt.% of calcium sulfosilicate; 1-5 wt% of dicalcium silicate and 1-8% of aluminoferrite mineral; 2 to 10 wt percent of free gypsum and 1 to 5 percent of free lime. The invention adopts the calcium sulfoaluminate-calcium sulfosilicate clinker with specific mineral composition as one of exciting agent materials, and can more effectively excite the activity of granulated blast furnace slag after being matched with anhydrite, which is characterized in that the setting time of cement is shortened by about 20 percent, and the early-stage fracture resistance and compressive strength of 1 and 3 days are improved by about 15 percent.
Description
Technical Field
The invention relates to slag sulphoaluminate cement and a production method thereof, in particular to a hydraulic cementing material with high early strength and short setting time and a production method thereof, belonging to the technical field of cement production.
Background
The granulated blast furnace slag is usually excited by a mixed excitation technology of alkali excitation and sulfate excitation, and the alkali excitation materials are usually lime, sodium hydroxide, sodium silicate, cement clinker and the like; the sulfate excitant mainly comprises: gypsum (anhydrite, calcined gypsum), and mirabilite. The activity of slag needs to be fully exerted in a certain alkaline environment after a certain amount of sulfate is added, and higher strength is obtained. SO in the presence of sulfate 4 2- With active Al in slag 2 O 3 And hydrated calcium aluminate to generate hydrated calcium sulfoaluminate (ettringite), and consuming a large amount of Ca in hydration liquid 2+ 、Al 3+ In turn, promotes slag hydration process, and the two actions promote each other.
In the existing production of slag sulphoaluminate cement, the used sulphoaluminate clinker takes anhydrous calcium sulphoaluminate and dicalcium silicate as main minerals, wherein the sum (mass fraction) of the anhydrous calcium sulphoaluminate and dicalcium silicate contents is not less than 60%, the anhydrous calcium sulphoaluminate content (mass fraction) is not less than 25%, and the dicalcium silicate content (mass fraction) is not less than 25%. At present, the clinker and the anhydrite are compounded to be used as an exciting agent, so that the exciting effect is very good, the physical properties of the cement are greatly improved and improved, but in the specific use process, the initial setting time and the final setting time of the cement are still longer than those of general cement, the early strength is lower than that of general cement, and the construction progress is influenced to a certain extent.
In the production of sulphoaluminate cement clinker, the transition mineral calcium sulphosilicate occurs, at 900-1200 ℃ and sometimes at temperatures up to 1300 ℃ a small amount of this mineral is present. It is often considered that this transition phase does not undergo hydration reaction or does so very slowly, however, in later studies, it was found that this mineral has hydration characteristics and that the high belite-calcium sulfoaluminate-calcium sulfosilicate clinker having a certain mineral composition exhibits characteristics of high early strength and rapid setting and hardening, and is thus highly paid attention to and a lot of experimental studies have been conducted.
In the prior art, the invention patent CN107827379A discloses high-fracture-resistance super-sulfate cement, which comprises the following raw materials: 65-90% of granulated blast furnace slag, 5-30% of gypsum and 0.5-7% of high belite sulphoaluminate cement clinker, wherein the mineral composition of the high belite sulphoaluminate cement clinker is 37-49% of belite, 20-37% of anhydrous calcium sulphoaluminate, 0.4-9% of tetra-calcium aluminoferrite, 6-26% of calcium sulfate and 0.5-4.6% of free calcium oxide. The activity of the granulated blast furnace slag can be effectively excited after the high belite sulphoaluminate cement clinker is combined with gypsum, the contribution of the granulated blast furnace slag to early and later mechanical properties of cement is fully exerted, the hydration hardening speed of the cement is greatly promoted, the early strength and the later strength, particularly the flexural strength are further improved, and the problems that the existing super-sulphate cement is low in early strength and easy to sand due to low hydration hardening speed are effectively solved. Specifically, the 1-day compressive strength of the cement reaches 18MPa, the 3-day compressive strength exceeds 40MPa, the 28-day compressive strength is higher than 80MPa, and the cement is far higher than ordinary Portland cement; the final setting time is 120-200 minutes, which accords with the national standard GB 175 and the specification of not more than 390 minutes for silicate cement. The slag excitation effect in the patent is good, higher early strength and shorter coagulation time are shown, but in fact, the quality difference of domestic slag resources is large, the use of a plurality of slag resources cannot reach the indexes, and the problems of long coagulation time, low early strength, difficult demoulding and the like are shown.
Therefore, on the basis of the prior art, the usability of the slag sulphoaluminate cement product still needs to be improved and improved to a certain extent, and the slag sulphoaluminate cement product is suitable for slag resources with different qualities, so that the effective utilization of industrial waste residues can be realized, the carbon emission is reduced, the better popularization and application can be obtained, and the technical requirements of engineering are met. Therefore, the invention combines the hydration mechanism of slag sulphoaluminate cement, and researches and develops a calcium sulphosilicate-sulphoaluminate clinker for producing slag sulphoaluminate cement.
Disclosure of Invention
The invention aims to provide slag sulphoaluminate cement, which adopts calcium sulphoaluminate-calcium sulphosilicate clinker with specific mineral composition as one of exciting agent materials, and more effectively excites the activity of granulated blast furnace slag after being matched with anhydrite, and has the technical effects of shortening the setting time of cement by about 20%, and improving the early-stage fracture resistance and compressive strength by about 15% in 1 and 3 days. Therefore, the invention also provides a production method of the slag sulphoaluminate cement.
The invention is realized by the following technical scheme: the slag sulphoaluminate cement comprises the following raw material components in percentage:
4-12% of calcium sulfoaluminate-calcium sulfosilicate cement clinker;
65-85% of granulated blast furnace slag or granulated blast furnace slag powder;
8 to 25 percent of anhydrite,
the mineral composition of the calcium sulfoaluminate-calcium sulfosilicate cement clinker meets the following conditions:
20-40 wt.% of anhydrous calcium sulfoaluminate, 30-55 wt wt.% of calcium sulfosilicate, and the sum of the contents of the anhydrous calcium sulfoaluminate and the calcium sulfosilicate is not less than 65 wt wt.%;
1-5. 5wt wt.% dicalcium silicate and 1-8 wt.% aluminoferrite mineral;
and III, 2-10 wt% of free gypsum and 1-5% of free lime.
The granulated blast furnace slag accords with GB/T203, and the granulated blast furnace slag powder accords with the regulations of S95 or S105 in GB/T18046-2017.
The anhydrite accords with class A secondary (containing) specified in GB/T5483-2008 and has sulfur trioxide content not less than 47 wt percent.
A method for producing the slag sulphoaluminate cement, comprising the following steps:
(1) The calcium sulfoaluminate-calcium sulfosilicate cement clinker and anhydrite are sent into a mill according to the proportion, and ground until the specific surface area is more than 420m 2 Kg, obtaining an excitant material;
(2) Using granulated blast furnace slag or granulated blast furnace slag powder, which is individually ground using a mill to a specific surface area of more than 400m 2 /kg；
(3) And (3) adding an exciting agent material into the ground granulated blast furnace slag or granulated blast furnace slag powder according to a proportion, and mixing by a mixing facility to obtain the slag sulphoaluminate cement.
The performance indexes of the slag sulphoaluminate cement meet the chemical and physical index requirements specified by the T/CBMF 192-2022 and T/CCPA 36-2022 slag sulphoaluminate cement.
The mill is a tubular ball mill or a vertical mill.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the calcium sulfoaluminate-calcium sulfosilicate clinker composed of specific minerals is adopted in the formula, and has a certain amount of free gypsum and free calcium, fine clinker crystals, loose structure and very strong activity, so that the calcium sulfoaluminate-calcium sulfosilicate clinker can quickly promote hydration reaction in cement, accelerate the disintegration of vitreous bodies in slag, quickly generate ettringite in early stage, and further fill the hydrated calcium silicate generated by continuous hydration in later stage into cement stone, so that the concrete is more compact and has higher strength. The overall appearance is that the setting time of the cement is shortened compared with the prior art, and the early strength is improved. The later strength, hydration heat, corrosion resistance coefficient and the like of the cement are basically the same as those of the prior art.
(2) The invention adopts the calcium sulfoaluminate-calcium sulfosilicate clinker, the clinker calcining temperature is lower than the existing clinker calcining technology by about 150 ℃, the coal consumption can be effectively reduced, and meanwhile, the clinker is loose, the grindability is good, the grinding electricity consumption is low, therefore, the product cost and the carbon emission can be further reduced, and the invention can be widely popularized and applied in marine corrosion-resistant engineering, mass concrete engineering, road and other engineering.
Drawings
FIG. 1 is a graph of a diffraction full spectrum fit quantitative analysis of a calcium sulfoaluminate-calcium sulfosilicate cement clinker according to the present invention.
Fig. 2 is a diagram of the diffraction mineral phase of the calcium sulfoaluminate-calcium sulfosilicate cement clinker of the present invention.
Fig. 3 is a scanning electron microscope photograph of the calcium sulfoaluminate-calcium sulfosilicate cement clinker of the present invention.
Detailed Description
The objects, technical solutions and advantageous effects of the present invention will be described in further detail below.
It is noted that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed, and unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention aims to provide slag sulphoaluminate cement prepared by taking calcium sulphoaluminate-calcium sulphosilicate clinker and anhydrite as exciting agent materials, wherein the adopted calcium sulphoaluminate-calcium sulphosilicate clinker is one of the exciting agent materials, has specific mineral composition, and can more effectively excite the activity of granulated blast furnace slag after being matched with gypsum when being compared with slag sulphoaluminate cement (the used clinker is also sulphoaluminate clinker with specific mineral composition such as Gaobalt-calcium sulphoaluminate clinker and the like) in the prior art, so that the setting time of cement is further shortened, the early strength of the cement is improved, and the later strength of the cement is also strongly ensured.
According to studies, it has been shown that the mineral composition of high belite-calcium sulfoaluminate cement clinker burned according to a certain mineral composition is: 15-35 wt% of anhydrous calcium sulfoaluminate, 5-25 wt% of calcium sulfosilicate, 40-70 wt% of dicalcium silicate, 3-8 wt% of aluminoferrite mineral, 2-15 wt% of free gypsum and 0-2 wt% of free lime, and the compressive strength of the prepared clinker is greater than 30MPa in 1 day and greater than 60MPa in 28 days.
The mineral composition of the adopted calcium sulfoaluminate-calcium sulfosilicate clinker is as follows: 20 to 40wt.% of anhydrous calcium sulfoaluminate, 30 to 55 wt wt.% of calcium sulfosilicate, 1 to 5wt.% of dicalcium silicate, 1 to 8wt.% of aluminoferrite mineral, 2 to 10 wt wt.% of free gypsum, and 1 to 5wt.% of free lime, and the sum of the contents of anhydrous calcium sulfoaluminate and calcium sulfosilicate is not less than 65 wt wt.%. Wherein, the mineral content of anhydrous calcium sulfoaluminate, calcium sulfosilicate and dicalcium silicate in the clinker is controlled, which is different from the existing high belite-calcium sulfoaluminate cement clinker, and is also more suitable for the excitant material of slag sulfoaluminate cement.
Specifically, the calcium sulfoaluminate-calcium sulfosilicate clinker adopted by the invention is calcined at about 1200 ℃, has a certain amount of free gypsum and free calcium, and the calcium sulfosilicate mineral has higher hydration activity than dicalcium silicate under a sulfoaluminate system, and the calcium sulfosilicate can provide C 2 S and CaSO 4 Moreover, the clinker has finer crystal, loose structure and strong activity, and can strongly excite and accelerate Ca in granulated blast furnace slag 2+ And A1O 2 － The dissolution rate of Ca dissolved out + And A1O 2 - Reacts with gypsum quickly to produce mineral ettringite with higher strength.
The calcium sulfoaluminate-calcium sulfosilicate clinker adopted in the invention is mainly prepared by selecting and proportioning calcareous raw materials (limestone), aluminous raw materials (kaolinite, fly ash, low-grade bauxite and red mud), siliceous raw materials (sandstone) and gypsum raw materials (phosphogypsum, desulfurized gypsum, natural gypsum and anhydrite). For example, limestone, low-grade alumina, phosphogypsum and sandstone=49:25:19:7 are selected, firstly raw materials are mixed according to the raw material proportion (mass ratio), the raw materials are put into a raw material mill for drying and grinding, then the ground raw materials are put into a cyclone preheater kiln with a pre-decomposition furnace for clinker calcination, the calcination temperature is controlled to be 1200+/-30 ℃, the required calcium sulfoaluminate-calcium sulfosilicate clinker (abbreviated as YT clinker) is obtained after cooling by a grate cooler, and the clinker is subjected to X-Ray diffraction quantitative analysis, wherein the mineral composition is shown as follows: 25.81wt.% anhydrous calcium sulfoaluminate, 48.57 wt wt.% calcium sulfosilicate, 2.44wt.% dicalcium silicate, 0.34wt.% aluminoferrite mineral, 9.7wt.% free gypsum, 1.61wt.% free lime, wherein the sum of the anhydrous calcium sulfoaluminate and calcium sulfosilicate content is 74.38 wt%. Referring specifically to fig. 1-3, the clinker has a mineral composition mainly of calcium sulfosilicate, calcium sulfoaluminate, free gypsum, gehlenite and the like, and an electron microscope photo shows that the clinker has even and loose minerals.
Furthermore, the granulated blast furnace slag adopted in the invention accords with GB/T203, and the granulated blast furnace slag powder accords with the regulations of S95 or S105 in GB/T18046-2017; the anhydrite accords with class A secondary (containing) specified in GB/T5483-2008 and the sulfur trioxide content is not less than 47 wt percent. And the performance indexes of the slag sulphoaluminate cement prepared by the invention all meet the chemical and physical index requirements specified by the T/CBMF 192-2022 and the T/CCPA 36-2022 slag sulphoaluminate cement.
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1: slag sulphoaluminate cement A1
The calcium sulfoaluminate-calcium sulfosilicate cement clinker and the anhydrite are sent into a tubular ball mill according to the mass ratio of 1:4, and ground to the specific surface area of 480m 2 Kg, obtaining an excitant material; grinding the granulated blast furnace slag by a ball mill to a specific surface area of 450m 2 /kg. The ground granulated blast furnace slag and the exciting agent material are mixed by a mixing facility according to the mass ratio of 3:1 to obtain slag sulphoaluminate cement A1, wherein YT clinker, anhydrite and mineral powder are in a ratio of=5:20:75.
Example 2: slag sulphoaluminate cement A2
The calcium sulfoaluminate-calcium sulfosilicate cement clinker and the anhydrite are sent into a tubular ball mill according to the mass ratio of 2:3, and ground to the specific surface area of 600m 2 Kg, obtaining an excitant material; the granulated blast furnace slag powder and the excitant material are mixed according to the mass ratio of 4:1 by using a mixing facility to obtain slag sulphoaluminate cement A2, YT clinker, anhydrite and mineral powder=8:12:80.
Example 3: slag sulphoaluminate cement A3
The calcium sulfoaluminate-calcium sulfosilicate cement clinker and anhydrite are sent into a vertical mill according to the mass ratio of 2:5, and ground to the specific surface area of 430m 2 Kg, obtaining an excitant material; grinding the granulated blast furnace slag by a ball mill to a specific surface area of 420m 2 /kg. The ground granulated blast furnace slag powder and the excitant material are according to the mass of 13:7The slag sulphoaluminate cement A3 is obtained after mixing by a mixing facility according to the weight ratio, wherein YT clinker, anhydrite and mineral powder=10:25:65.
Example 4: slag sulphoaluminate cement A4
The calcium sulfoaluminate-calcium sulfosilicate cement clinker and anhydrite are sent into a vertical mill to be sent into a tubular ball mill according to the mass ratio of 4:11, and ground to the specific surface area of 500m 2 Kg, obtaining an excitant material; grinding the granulated blast furnace slag by a ball mill to a specific surface area of 450m 2 /kg. The ground granulated blast furnace slag powder and the excitant material are mixed by a mixing facility according to the mass ratio of 17:3 to obtain slag sulphoaluminate cement A4, wherein YT clinker, anhydrite and mineral powder=4:11:85.
Example 5: slag sulphoaluminate cement A5
The calcium sulfoaluminate-calcium sulfosilicate cement clinker and anhydrite are sent into a vertical mill according to the mass ratio of 1:2, and ground to the specific surface area of 450m 2 Kg, obtaining an excitant material; the granulated blast furnace slag powder and the exciting agent are mixed by a mixing facility according to the mass ratio of 19:6 to obtain slag sulphoaluminate cement A5, wherein YT clinker, anhydrite and mineral powder=8:16:76.
Example 6: slag sulphoaluminate cement A6
The calcium sulfoaluminate-calcium sulfosilicate cement clinker and the anhydrite are sent into a tubular ball mill according to the mass ratio of 2:5, and ground to the specific surface area of 450m 2 Kg, obtaining an excitant material; grinding the granulated blast furnace slag by a ball mill to a specific surface area of 420m 2 /kg. The ground granulated blast furnace slag and the excitant material are mixed by a mixing facility according to the mass ratio of 18:7 to obtain slag sulphoaluminate cement A6, wherein YT clinker, anhydrite and mineral powder are in a ratio of 8:20:72.
Example 7: slag sulphoaluminate cement A7
The calcium sulfoaluminate-calcium sulfosilicate cement clinker and the anhydrite are sent into a tubular ball mill according to the mass ratio of 3:2, and ground to the specific surface area of 550m 2 Kg, obtaining an excitant material; granulating the above blast furnaceThe slag is singly ground by a ball mill until the specific surface area is 420m 2 /kg. The ground granulated blast furnace slag and the excitant material are mixed by a mixing facility according to the mass ratio of 4:1 to obtain slag sulphoaluminate cement A7, wherein YT clinker, anhydrite and mineral powder are in a ratio of 12:8:80.
Example 8: slag sulphoaluminate cement A8
The calcium sulfoaluminate-calcium sulfosilicate cement clinker and the anhydrite are sent into a tubular ball mill according to the mass ratio of 1:2, and ground to the specific surface area of 460m 2 Kg, obtaining an excitant material; the granulated blast furnace slag powder and the excitant are adopted according to the following steps of 16:9, and mixing by a mixing facility to obtain slag sulphoaluminate cement A8, wherein YT clinker, anhydrite and mineral powder=12:24:64.
Comparative example 1: slag sulphoaluminate cement B1
According to the production method and the raw material proportion of the embodiment 1, sulfoaluminate clinker (meeting the standard requirements of T/CBMF 192-2022 and T/CCPA 36-2022) is mixed with anhydrite for grinding, and then the mixture is added into the ground granulated blast furnace slag to prepare slag sulfoaluminate cement B1, wherein the sulfoaluminate clinker, the anhydrite and mineral powder are respectively equal to 5:20:75.
Comparative example 2: slag sulphoaluminate cement B2
According to the production method of example 1, high belite-calcium sulfoaluminate cement clinker (BYT) (the mineral composition of which is 15-35 wt percent of anhydrous calcium sulfoaluminate, 5-25 wt percent of calcium sulfosilicate, 40-70 wt percent of dicalcium silicate, 3-8 wt percent of aluminoferrite mineral, 2-15 wt percent of free gypsum and 0-2 wt percent of free lime) is adopted to mix and grind with anhydrite, and then added into the ground granulated blast furnace slag to prepare slag sulfoaluminate cement B2, wherein BYT clinker, anhydrite and mineral powder are in a ratio of=5:20:75.
Slag sulfoaluminate cements A1 to A8 of the above examples 1 to 8, and slag sulfoaluminate cements B1 and B2 of comparative examples 1 and 2 were taken, respectively, and the cements were subjected to test block forming and curing according to the GB/T17671-2021 cement mortar strength test method (ISO method).
(one) Strength test
The strength detection is carried out by using a bending and compression resistant integrated machine by adopting a GB/T17671-2021 cement mortar strength detection method (ISO method). The test results are shown in table 1 below.
TABLE 1
As is apparent from Table 1 above, the slag sulfoaluminate cements of the present invention have about 15% improvement in the flexural/compressive strength of 1d and 3d, and about the same level in the flexural/compressive strength of 28d and 90d, as compared with the comparative examples.
(II) determination of coagulation time
The setting time was determined according to GB/T1346-2011 method for testing the water consumption, setting time and stability of Cement Standard consistencies. The test results are shown in table 2 below.
TABLE 2
As is clear from Table 2 above, the slag sulphoaluminate cement of the present invention has an initial setting time shortened by about 20% and a final setting time shortened by about 15% as compared with the comparative example.
(III) determination of hydration Heat and Corrosion resistance coefficient
The hydration heat test is carried out according to GB/T12959-2008 method for measuring hydration heat of Cement.
The corrosion resistance coefficient test was carried out according to the immersion corrosion resistance test method (K method) specified in GB/T749-2008, test method for sulfate corrosion resistance of Cement, chapter 4.
The test results are shown in table 3 below.
TABLE 3 Table 3
As is clear from Table 3 above, the hydration heat of 3d and 7d is substantially leveled and the corrosion resistance coefficient of 28d is also substantially leveled in the slag sulphoaluminate cement of the present invention as compared with the comparative example.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation, etc. of the above embodiment according to the technical matter of the present invention fall within the scope of the present invention.
Claims (6)
1. A slag sulphoaluminate cement, characterized in that: comprises the following raw material components in percentage by weight:
4-12% of calcium sulfoaluminate-calcium sulfosilicate cement clinker;
65-85% of granulated blast furnace slag or granulated blast furnace slag powder;
8 to 25 percent of anhydrite,
the mineral composition of the calcium sulfoaluminate-calcium sulfosilicate cement clinker meets the following conditions:
20-40 wt.% of anhydrous calcium sulfoaluminate, 30-55 wt wt.% of calcium sulfosilicate, and the sum of the contents of the anhydrous calcium sulfoaluminate and the calcium sulfosilicate is not less than 65 wt wt.%;
1-5. 5wt wt.% dicalcium silicate and 1-8 wt.% aluminoferrite mineral;
and III, 2-10 wt% of free gypsum and 1-5% of free lime.
2. The slag sulfoaluminate cement according to claim 1, wherein: the granulated blast furnace slag accords with GB/T203, and the granulated blast furnace slag powder accords with the regulations of S95 or S105 in GB/T18046-2017.
3. The slag sulfoaluminate cement according to claim 1, wherein: the anhydrite accords with class A secondary (containing) specified in GB/T5483-2008 and has sulfur trioxide content not less than 47 wt percent.
4. A method for producing the slag sulfoaluminate cement of any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) The calcium sulfoaluminate-calcium sulfosilicate cement clinker and anhydrite are sent into a mill according to the proportion, and ground until the specific surface area is more than 420m 2 Kg, obtainedObtaining an excitant material;
(2) Using granulated blast furnace slag or granulated blast furnace slag powder, which is individually ground using a mill to a specific surface area of more than 400m 2 /kg；
(3) And (3) adding an exciting agent material into the ground granulated blast furnace slag or granulated blast furnace slag powder according to a proportion, and mixing by a mixing facility to obtain the slag sulphoaluminate cement.
5. The production method according to claim 4, wherein: the performance indexes of the slag sulphoaluminate cement meet the chemical and physical index requirements specified by the T/CBMF 192-2022 and T/CCPA 36-2022 slag sulphoaluminate cement.
6. The production method according to claim 4, wherein: the mill is a tubular ball mill or a vertical mill.
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