CN107021654B - A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof - Google Patents
A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof Download PDFInfo
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- CN107021654B CN107021654B CN201710400866.5A CN201710400866A CN107021654B CN 107021654 B CN107021654 B CN 107021654B CN 201710400866 A CN201710400866 A CN 201710400866A CN 107021654 B CN107021654 B CN 107021654B
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- 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
- C04B7/32—Aluminous cements
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- 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
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- 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
- C04B7/47—Cooling ; Waste heat management
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof, the main mine of the clinker of the cement mutually includes following component in parts by mass: C4(A x F 1‑x )35 ~ 40 parts of $, C5S220 ~ 65 parts of $, 5 ~ 15 parts of C $, C35 ~ 20 parts of A.Preparation method is to calcine cement slurry next time at 1050 ~ 1200 DEG C, and keep the temperature and be made no more than 1h.The present invention largely reduces clinker preparation energy consumption and CO2Discharge amount, and the clinker being burnt into has good grindability.Sulphur calcium silicates sulphate aluminium cement shows good early mechanics characteristics, calcium sulfoaluminate minerals basic aquation in 7d is complete, aquation is had begun when sulphur calcium silicates mineral 7d, solve the problems, such as sulphate aluminium cement later strength retraction, the dihydrate gypsum that sulphur calcium silicates aquation generates can calcium trisulphoaluminate hydrate converted to single sulfur type hydrated calcium aluminate sulfate.
Description
Technical field
The invention belongs to cement preparation technical fields, and in particular to a kind of sulphur calcium silicates sulphate aluminium cement and its preparation side
Method.
Background technique
High sulfur type hydrated calcium aluminate sulfate is one of main hydration products of sulphate aluminium cement, and sulphate aluminium cement
Intensity is mainly provided by high sulfur type hydrated calcium aluminate sulfate.With the progress of sulphate aluminium cement aquation, calcium sulfate is gradually used up
It finishes, SO in hardened paste hole solution4 2-Concentration reduces, and high sulfur type hydrated calcium aluminate sulfate is converted to low sulfur type hydrated calcium aluminate sulfate,
Lead to sulphate aluminium cement later strength retraction.Therefore, improve sulphate aluminium cement later strength to grind as sulphate aluminium cement
The focus studied carefully.
Sulphur calcium silicates mineral are one of sulphoaluminate cement clinker calcination process intermediate products, in previous research
In, sulphur calcium silicates has always been considered as being a kind of low hydration activity even inert mineral, and formation temperature range is 1050 DEG C-
1200 DEG C, and the calcination temperature of sulphoaluminate cement clinker is 1250 DEG C or more, in the temperature, sulphur calcium silicates mineral can thoroughly divide
Solution forms belite and anhydrite.Research accordingly, with respect to sulphur calcium silicates mineral is very few.Applicants have found that in sulphur aluminic acid
In salt cement gelling system, sulphur calcium silicates mineral have hydration activity more higher than belite mineral, the sulphur aluminium of sulfur-bearing calcium silicates
Acid salt cement aquation later strength shows the trend of sustainable growth.In addition, the progress of the aquation with sulphur calcium silicates mineral,
Sulphur calcium silicates mineral release a small amount of dihydrate gypsum, so that sulfate concentration improves in the hole solution of hardened cement paste, suppression
Conversion of the high sulfur type hydrated calcium aluminate sulfate to low sulfur type hydrated calcium aluminate sulfate is made.Therefore, sulphur calcium silicates mineral can be introduced into
In sulphate aluminium cement system, sulphate aluminium cement later strength retraction is solved the problems, such as.
The calcination temperature of sulphoaluminate cement clinker is at 1250 DEG C or more, and in order to make in sulphoaluminate cement clinker, there are sulphur
Calcium silicates mineral, it usually needs promote the formation of sulphur calcium silicates mineral at a temperature of lower secondary clacining, this is to a certain degree
On increase the preparation energy consumption and CO of sulfur-bearing calcium silicates sulphoaluminate cement clinker2Discharge amount.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of sulphur calcium silicates aluminium sulfate water
Mud and preparation method thereof, it is intended to reduce the calcinating consumption and CO of sulphoaluminate cement clinker2Discharge amount, and sulphur calcium silicates sulphur aluminium
Acid salt cement shows good early stage and later period mechanical property, and the aquation of sulphur calcium silicates mineral solves sulphate aluminium cement
The problem of later strength retraction and high sulfur type hydrated calcium aluminate sulfate are converted to single sulfur type hydrated calcium aluminate sulfate.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of sulphur calcium silicates sulphate aluminium cement, the main mine of clinker mutually include in parts by mass such as the following group
Point: C4(A x F 1-x )35 ~ 40 parts of $, C5S220 ~ 65 parts of $, 5 ~ 15 parts of C $, C35 ~ 20 parts of A, wherein 0 < x < 0.5.F is Fe2O3's
Abbreviation, that A is represented is Al2O3, $ represents element sulphur, and S then represents silicon.
It wherein, further include the secondary phase C for being not more than 10 parts2S。
The C4(A x F 1-x )3$ is C4A 3 $。
The sulphur calcium silicates sulphoaluminate cement clinker has good grindability.The sulphur calcium silicates sulphate aluminium cement
In C4(A x F 1-x )3$ mineral have high hydration activity, the C in hydration age to 7d, cement4(A x F 1-x )3$ is substantially
Complete aquation.When 7d, sulphur calcium silicates mineral have begun aquation, maintain good later period mechanical property.
A kind of preparation method of above-mentioned sulphur calcium silicates sulphate aluminium cement, clinker be cement slurry 1050 ~
1200 DEG C are calcined next time, and are kept the temperature and be made no more than 1h.
Specifically includes the following steps:
The preparation of S1, cement slurry: lime stone, ardealite, aluminiferous material, flyash are mixed, then cross 100 through grinding
Cement slurry is made in mesh；The aluminiferous material is kaolin or alumina.
The preparation of S2, clinker: the cement slurry that S1 is obtained is placed in high temperature furnace, then high temperature furnace is risen to from room temperature
1130 ~ 1150 DEG C, and calcined in 30 ~ 60min of heat preservation at this temperature to get clinker, then clinker is placed in
It carries out air-cooled in air, is cooled to room temperature to get to sulphur calcium silicates sulphate aluminium cement.
Wherein, lime stone described in S1, ardealite, aluminiferous material, flyash be respectively as follows: in parts by mass 67 ~ 72 parts,
40 ~ 44 parts, 6. ~ 40 parts, 0.45 ~ 19 part.
The temperature that initially forms of calcium sulfoaluminate minerals is 1050 DEG C in sulphoaluminate cement clinker, and being sufficiently formed temperature is
1250 DEG C, in order to be sufficiently formed calcium sulfoaluminate minerals within the scope of the best formation temperature of sulphur calcium silicates mineral, the present invention is reduced
The content of calcium sulphoaluminate mine phase in sulphoaluminate cement clinker, and introduce sulphur calcium silicates mineral and tricalcium aluminate mineral.It is low
The two components of Wen Shi, gypsum and aluminium oxide are excessive, can promote being sufficiently formed for calcium sulphoaluminate mine phase.Meanwhile in low temperature, residue
Aluminum component can be adequately formed tricalcium aluminate, anhydrite can be adequately formed sulphur calcium silicates mineral or in the form of anhydrite
In the presence of foring sulphur calcium silicates sulphoaluminate cement clinker system.Not only reduce the calcination temperature of sulphoaluminate cement clinker
And CO2The mechanical property of sulphur calcium silicates sulphate aluminium cement can be improved in discharge amount, the C-S-H gel that sulphur calcium silicates mineral aquation generates
Can, meanwhile, the calcium sulphate dihydrate of generation is able to suppress high sulfur type hydrated calcium aluminate sulfate and converts to single sulfur type hydrated calcium aluminate sulfate, most
Calcium sulphoaluminate-sulphur calcium silicates-tricalcium aluminate-anhydrite cement clinker is obtained eventually.
Compared with prior art, the invention has the following beneficial effects:
1, the calcination temperature of sulphur calcium silicates sulphoaluminate cement clinker is low, can be effectively reduced the energy of clinker preparation
Consumption.
2, belite mine phase and iron aluminium phase content are extremely low in sulphur calcium silicates sulphate aluminium cement mud clinker, and grindability is good, energy
The energy consumption and CO being enough effectively reduced in cement pulverizing course2Discharge amount
3, contain a large amount of sulphur calcium silicates mineral in sulphur calcium silicates sulphoaluminate cement clinker, be able to solve common sulphur aluminic acid
The problem of salt cement later strength retraction, sulphate aluminium cement later strength shows the trend of growth.
4, aluminum component needed for sulphur calcium silicates sulphoaluminate cement clinker is few, sulphur component is more, therefore, low-grade bauxite with
And the industrial solid castoff containing aluminium can provide aluminum component for the calcining of the clinker, and can largely utilize sulfur acid calcium
Industrial solid castoff, such as: ardealite, fluorgypsum, lemon gypsum.
5, sulphur calcium silicates sulphoaluminate cement clinker has good grindability.
6, the C in sulphur calcium silicates sulphate aluminium cement4(A x F 1-x )3$ mineral have high hydration activity, work as hydration age
C to 7d, in cement4(A x F 1-x )3$ substantially completely aquation.When 7d, sulphur calcium silicates mineral have begun aquation, and aquation generates
C-S-H gel the mechanical property of sulphur calcium silicates sulphate aluminium cement can be improved, meanwhile, the calcium sulphate dihydrate of generation is able to suppress
High sulfur type hydrated calcium aluminate sulfate is converted to single sulfur type hydrated calcium aluminate sulfate.
Detailed description of the invention
Fig. 1 is the clinker XRD spectrum of embodiment one；
Fig. 2 is the clinker XRD spectrum of embodiment two；
Fig. 3 is the clinker XRD spectrum of embodiment three；
Fig. 4 is the clinker and belite sulphate aluminium cement particle volume comparison diagram of embodiment three；
Fig. 5 is the clinker and belite sulphate aluminium cement net slurry compression strength comparison diagram of embodiment three；
Fig. 6 is the clinker net slurry hydrated product XRD spectrum of embodiment three.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment one
Sulphur calcium silicates sulphate aluminium cement is prepared in the following manner:
A, the preparation of cement slurry
By 71.39 mass parts lime stones, 43.34 mass parts ardealites, 6.22 mass parts kaolin, 18.24 mass parts powder
Coal ash mixing, then sieves with 100 mesh sieve the raw grinding matched, and cement slurry is made.
B, the preparation of clinker
Raw material obtained in A are placed in high temperature furnace and are calcined, high temperature furnace rises to 1130 DEG C from room temperature, and keeps the temperature at 1130 DEG C
Then clinker is taken out chilling in air by 30min from high temperature furnace, obtain sulphur calcium silicates sulphoaluminate cement clinker, and Fig. 1 is
The XRD spectrum of the clinker of this implementation.Through Rietveld quantitative analysis, the mineral composition of clinker are as follows: C4A3$:
21.26%、C5$2S:60.41%, C3A:8.05% C $: 7.79, C2S:2.49%。
Embodiment two
Sulphur calcium silicates sulphate aluminium cement is prepared in the following manner:
A, the preparation of cement slurry
By 67.64 mass parts lime stones, 40.67 mass parts ardealites, 38.84 mass parts alumina, 0.48 mass parts fine coal
Ash mixing, then sieves with 100 mesh sieve the raw grinding matched, and cement slurry is made.
B, the preparation of clinker
Raw material obtained in A are placed in high temperature furnace and are calcined, high temperature furnace rises to 1130 DEG C from room temperature, and keeps the temperature at 1130 DEG C
Then clinker is taken out chilling in air by 60min from high temperature furnace, obtain sulphur calcium silicates sulphoaluminate cement clinker, and Fig. 2 is
The XRD spectrum of the clinker of this implementation.Through Rietveld quantitative analysis, the mineral composition of clinker are as follows: C4A3$:
36.21%、C5$2S:42.00%, C3A:9.21 C $: 5.83%, C2S:6.75%。
Embodiment three
Sulphur calcium silicates sulphate aluminium cement is prepared in the following manner:
A, the preparation of cement slurry
By 67.64 mass parts lime stones, 40.67 mass parts fluorgypsums, 38.84 mass parts alumina, 0.48 mass parts fine coal
Ash mixing, then sieves with 100 mesh sieve the raw grinding matched, and cement slurry is made.
B, the preparation of clinker
Raw material obtained in A are placed in high temperature furnace and are calcined, high temperature furnace rises to 1150 DEG C from room temperature, and keeps the temperature at 1150 DEG C
Then clinker is taken out chilling in air by 60min from high temperature furnace, obtain sulphur calcium silicates sulphoaluminate cement clinker, and Fig. 3 is
The XRD spectrum of the clinker of this implementation.Through Rietveld quantitative analysis, the mineral composition of clinker are as follows: C4A3$:
35.17%、C5$2S:45.58%, C3A:10.02 C $: 8.79, C2S:0.44%。
C, 10% natural gypsum is added in the clinker being burnt into B, being milled to specific surface area through ball mill is 350m2/kg。
D, the cement clinker particles volume that the present embodiment is prepared as shown in Figure 4 (in figure, TCSA: sulphur calcium silicates sulphur aluminium
Sour water mud；BCSA: belite sulphate aluminium cement).Taking particle size respectively is 2-5 μm of sulphur calcium silicates sulphur aluminic acid cement
Clinker and belite sulphoaluminate cement clinker, while grinding is carried out with planetary ball mill, and measure cement after measurement powder
The size distribution of clinker.After 20min grinding, sulphur calcium silicates sulphoaluminate cement clinker powder and belite sulphur silicic acid
The specific surface area of calcium sulphoaluminate cement clinker grinding distinguishes 3624cm2/ g and 1719cm2/g.As seen from the figure, sulphur calcium silicates sulphur
Aluminic acid cement has good grindability compared to belite sulphate aluminium cement.
E, the cement paste compression strength that the present embodiment is prepared (TCSA: sulphur calcium silicates sulphur aluminic acid water as shown in Figure 5
Mud；BCSA: belite sulphate aluminium cement), wherein the ratio of mud of cement paste is 0.4；The maintenance item of concrete paste specimen
Part is supported for water, and temperature is 20 DEG C.
As seen from the figure, belite sulphate aluminium cement net slurry early anti pressured intension is significantly lower than sulphur calcium silicates sulphur aluminic acid
Salt water cement paste compression strength.After mixing 10% gypsum, sulphur calcium silicates sulphate aluminium cement net slurry compression strength does not add stone
The net slurry compression strength of cream clinker wants high.Also there is not retraction in 28d compression strength, and presents the trend of growth.
F, the present embodiment is prepared cement paste hydrated product XRD spectrum as shown in fig. 6, come as seen from the figure,
Calcium sulphoaluminate is in 7d, substantially completely aquation, and therefore, the growth of cement paste compression strength can be attributed to the fact that sulphur after 7d
The aquation of calcium silicates mineral.
The above embodiment of the present invention is only example to illustrate the invention, and is not to implementation of the invention
The restriction of mode.For those of ordinary skill in the art, other can also be made not on the basis of the above description
With the variation and variation of form.Here all embodiments can not be exhaustive.It is all to belong to technical solution of the present invention
Changes and variations that derived from are still in the scope of protection of the present invention.
Claims (3)
1. a kind of preparation method of sulphur calcium silicates sulphate aluminium cement, which comprises the following steps:
The preparation of S1, cement slurry
By lime stone, ardealite, aluminiferous material, flyash be respectively as follows: in parts by mass 67 ~ 72 parts, 40 ~ 44 parts, 6 ~ 40 parts,
0.45 ~ 19 part of mixing, then sieves with 100 mesh sieve through grinding, cement slurry is made；The aluminiferous material is kaolin or alumina；
The preparation of S2, clinker
The cement slurry that S1 is obtained is placed in high temperature furnace, then high temperature furnace is risen to 1130 ~ 1150 DEG C from room temperature, and in the temperature
30 ~ 60min of lower heat preservation is calcined to get clinker, and clinker is placed in cooling in air after calcining, is cooled to
Room temperature to get arrive sulphur calcium silicates sulphate aluminium cement；
The main mine of clinker mutually includes following component in parts by mass: C4(A x F 1-x )35 ~ 40 parts of $, C5S2$ 20~65
Part, 5 ~ 15 parts of C $, C35 ~ 20 parts of A, wherein 0 < x < 0.5.
2. the preparation method of sulphur calcium silicates sulphate aluminium cement according to claim 1, which is characterized in that further include being not more than
10 parts of secondary phase C2S。
3. the preparation method of sulphur calcium silicates sulphate aluminium cement according to claim 1, which is characterized in that the C4
(AxF1-x)3$ is C4A3$。
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| CN108793785B (en) * | 2018-07-24 | 2021-07-13 | 盐城工学院 | Low-temperature preparation method of sulfosilicate-belite-sulphoaluminate cement |
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| CN110498631A (en) * | 2019-08-30 | 2019-11-26 | 北京工业大学 | A method of improving sulphate aluminium cement stable long-term strength |
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| CN114213043B (en) * | 2022-01-06 | 2022-09-06 | 南京工业大学 | High belite-calcium sulfoaluminate-calcium sulfosilicate cement clinker and preparation method thereof |
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| CN115925291B (en) * | 2022-11-19 | 2024-03-12 | 济南大学 | Low-calcium multi-element cement clinker capable of efficiently utilizing phosphogypsum and preparation method thereof |
| CN115849740B (en) * | 2022-12-07 | 2024-03-29 | 中国建筑材料科学研究总院有限公司 | Dicalcium silicate-calcium sulfoaluminate-calcium sulfosilicate cement clinker and preparation process thereof |
| CN115959844A (en) * | 2023-02-07 | 2023-04-14 | 康达(湖南)水泥有限公司 | Method for preparing cement by using phosphogypsum |
| CN116354628A (en) * | 2023-03-20 | 2023-06-30 | 重庆大学 | Method for preparing calcium silicate-calcium sulfoaluminate cement |
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| CN104609750A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Sulphoaluminate cement and preparation method thereof |
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