CN108314344A - A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker - Google Patents
A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker Download PDFInfo
- Publication number
- CN108314344A CN108314344A CN201810069431.1A CN201810069431A CN108314344A CN 108314344 A CN108314344 A CN 108314344A CN 201810069431 A CN201810069431 A CN 201810069431A CN 108314344 A CN108314344 A CN 108314344A
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- China
- Prior art keywords
- phosphorus
- sulphur
- clinker
- calcium silicate
- cement
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Classifications
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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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/02—Phosphate cements
- C04B12/027—Phosphate cements mixtures thereof with other inorganic cementitious materials
-
- 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
Abstract
The invention discloses a kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, which can realize C at lower calcining temperatures4A3$、C4AF, phosphorus calcium aluminate and 2C2SC $ coexist.Present invention introduces phosphorus calcium aluminates to replace part calcium sulphoaluminate so that there is the more common sulphate aluminium cement of the present invention higher early strength and later strength growth, enough sulphur and iron content also to effectively reduce the formation temperature of high temperature mine phase phosphorus calcium aluminate.Sulphur calcium silicates is instead of C2S so that the present invention can be burnt under lower calcination temperature, and have good grindability, while the CaSO that sulphur calcium silicates aquation is formed4·2H2O can effectively solve the problem that sulphate aluminium cement later strength retraction problem.In addition, the present invention is also rich in more iron phase, the firing temperature of the present invention is integrally reduced, and the iron glue that its aquation is formed imparts good cementability of the invention and wear-resistant, scour resistance, can be used for the repairing operation of ocean engineering.
Description
Technical field
The present invention designs a kind of cement material, and in particular to a kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker and its system
Preparation Method.
Background technology
People are usually known as by sulphate aluminium cement and ferrous aluminate cement and by their other derivative cement types
Third series cement, the series cement clinker are mainly characterized by mineral composition and contain a large amount of C4A3$, special clinker composition and water
The features such as changing product makes the series cement have early by force, high-strength, anti-corrosion, freeze proof, impervious and microdilatancy.By adjusting clinker,
The volume of gypsum and admixture three, the different cement type of availability.Third series cement from be born 50 years so far,
It is widely used in China, but its research is never stopped, third series cement still has large development space
And potentiality.
In patent《A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof》In (publication number 107021654A), Qian Jue
When et al. by optimizing raw material formula and reduce clinker firing temperature to 1050~1200 DEG C, make in sulphate aluminium cement
C2S remains at a phase state, i.e., undecomposed sulphur calcium silicates.Sulphur calcium silicates has preferable grindability, and can be in water
The aquation later stage of mud carries out aquation, forms C-S-H gels and provides later strength, and release calcium sulphate dihydrate, prevents sulphur aluminic acid
Calcium trisulphoaluminate hydrate (AFt) in salt cement is converted to single sulfur type hydrated calcium aluminate sulfate (AFm), is avoided because of aquation sulphur
Later stage strength of cement retraction problem caused by calcium aluminate phase transformation.
Phosphor aluminate cement has early strengthening and high strengthening, corrosion-resistant, freeze thawing resistance resistance to as a kind of novel extraordinary cementitious material
The features such as high temperature, basicity is low.But phosphor aluminate cement firing temperature is high and needs to make mineralizer using MgO when calcining, cost compared with
It is high.Patent《High ferro phosphoaluminate clinker》A kind of high ferro phosphorus aluminic acid is referred in (patent publication No. CN 104140216A)
Salt cement not only reduces the burning of phosphor aluminate cement using a large amount of brown iron oxide and scum instead of expensive MgO
At temperature, the performance of cement is gone back while improved.Not only remain the fast solidifying of phosphor aluminate cement, early strong, anti-ion erosion etc.
The characteristics of feature, the introducing of ferrous aluminate impart the cement microdilatancy again, rub resistance.
Invention content
The purpose of the present invention is to provide a kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, which passes through two
Prepared by secondary calcine technology, realize phosphorus calcium aluminate, sulphur calcium silicates, C4A3$ and C4AF's coexists.Phosphorus sulphate aluminium cement is in sulphur
Being introduced in aluminate cement system in right amount there is excellent early stage mutually to be formed with later stage mechanics, corrosion resistance phosphorus calcium aluminate mine outstanding
, hydrated product compact structure, cohesive force is strong, and scour resistance is good；But it needs high-quality aluminum raw material.In order to reduce its aluminium
Composition ratio saves fine aluminum resource consumption, and the present invention is reduced in blending process in clinker based on phosphorus sulphate aluminium cement
Calcium sulphoaluminate ratio forms the sulphur silicon of part early hydration function admirable using secondary clacining technique in phosphorus sulphate aluminium cement
Sour calcium mine phase reaches saving bauxite resource, optimizes its mechanics for compensating the early mechanics characteristics loss for reducing calcium sulphoaluminate and bringing
The purpose of performance.
The present invention also provides the preparation methods of above-mentioned sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, using secondary clacining
Technique prepares sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, by the phosphorus sulphate aluminium cement obtained after primary calcining with gypsum one
It rises and carries out secondary clacining, the C in cement2S is converted into sulphur calcium silicates.Sulphur calcium silicates has been found can be with aquation, and its aquation
Activity ratio C2S high can provide preferable prometaphase intensity.
The present invention uses following technical scheme：
A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, raw material chemical content percentage composition are as follows：CaO 40
~50%, Al2O325~35%, Fe2O34~6%, SiO25~8%, SO38~11%, P2O51.5~2.3%, ZnO
0.8~1%.
Preferably, the sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, the mineral composition of clinker include：10
~15% phosphorus calcium aluminate, 20~35% sulphur calcium silicates, C4A3$ 30~45%, C4The interphase of AF 10~20% and 2~10%.
A kind of preparation method of above-mentioned sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, it includes the following steps：
A) weighing dispensing is carried out by composition of raw materials, carries out first time calcining after mixing, and keep the temperature 1-2h；
B) by after the semi-finished product clinker grinding obtained by step a), incorporation is equivalent to the stone of semi-finished product clinker quality 6~11%
Cream, then secondary low temperature calcination is carried out, obtain sulphur calcium silicate types phosphorus sulphate aluminium cement after keeping the temperature 1-2h.
Preferably, first time calcination temperature is 1360~1380 DEG C, and second of calcination temperature is 1150~1200 DEG C.
The beneficial effects of the invention are as follows：1) present invention contain independent phosphorus calcium aluminate mine phase, account for about mass fraction 10~
15%, this give present invention early stage outstanding and later stage mechanical properties, and its aquation forms C-A-P-H gels and improves cement
Condensation performance and have certain chlorion ability to cure.2) contain a large amount of iron phases in dispensing, with the SO in raw material3, ZnO it is total
With composite mineralizer is played, the firing temperature of high temperature mine phase phosphorus calcium aluminate, C can be effectively reduced4The iron glue that AF aquations are formed
This cement adhesive property and anti-erosion property are more highlighted, rapid rush-repair and the maintenance of ocean engineering are can be used for.3) present invention two
When secondary calcining, by mixing proper amount of gypsum, cement ore phase composition is improved, so that the waste residue of sulfur acid calcium is applied, always
The consumption to the high aluminas raw material such as bauxite is also reduced on body.The use of composite mineralizer and secondary clacining technique, realize
By phosphorus calcium aluminate, C4A3$, sulphur calcium silicates and C4System coexists in the novel concrete of tetra- kinds of main mine phase compositions of AF, makes aluminium sulfate
The cement prometaphase, intensity further improved, and water mudrock structure is finer and close, and corrosion resistance is excellent.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, raw material chemical composition is when once calcining：CaO
38.8%, Al2O327.6%, Fe2O34.3%, SiO27.5%, SO35.1%, P2O51.7% and 1%ZnO, by design ratio
Example mixing, firing temperature are set as 1360 DEG C, soaking time 1 hour；Incorporation is equivalent to the two of its quality 11% after semi-finished product cooling
Water gypsum grinding mixing carries out secondary clacining, soaking time 1 hour at 1150 DEG C.The clinker setting time of preparation and mechanics
Performance is as shown in table 1, and anti-erosion property is as shown in table 2.
Embodiment 2
A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, raw material chemical composition is when once calcining：CaO
39.2%, Al2O326.8%, Fe2O34.8%, SiO27.4%, SO35.0%, P2O51.8% and 1%ZnO, by design ratio
Example mixing, firing temperature are set as 1370 DEG C, soaking time 1 hour；Incorporation is equivalent to the two of its quality 10% after semi-finished product cooling
Water gypsum grinding mixing carries out secondary clacining, soaking time 1 hour at 1150 DEG C.The clinker setting time of preparation and mechanics
Performance is as shown in table 1, and anti-erosion property is as shown in table 2.
Embodiment 3
A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, raw material chemical composition is when once calcining：CaO
36.7%, Al2O339.4%, Fe2O35.2%, SiO26.9%, SO34.8%, P2O52.0% and 1%ZnO, by design ratio
Example mixing, firing temperature are set as 1370 DEG C, soaking time 1 hour；Incorporation is equivalent to the two of its quality 13% after semi-finished product cooling
Water gypsum grinding mixing carries out secondary clacining, soaking time 1 hour at 1150 DEG C.The clinker setting time of preparation and mechanics
Performance is as shown in table 1, and anti-erosion property is as shown in table 2.
Embodiment 4
A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker clinker, raw material chemical composition is when once calcining：CaO
41.5%, Al2O325.7%, Fe2O35.9%, SiO26.2%, SO33.5%, P2O52.2% and 1%ZnO, by design ratio
Example mixing, firing temperature are set as 1380 DEG C, soaking time 1 hour；Incorporation is equivalent to two water of its quality 9% after semi-finished product cooling
Gypsum grinding mixing carries out secondary clacining, soaking time 1 hour at 1150 DEG C.The clinker setting time of preparation and mechanical property
Can as shown in table 1, anti-erosion property is as shown in table 2.
Comparative example 1
Commercially available common sulphate aluminium cement, raw material chemical composition degree are：CaO 36~43%, Al2O3 28
~40%, SiO23~10%, SO38~15%, Fe2O31~3%.
The setting time of 1 clinker of table and mechanical property
The anti-erosion property of 2 clinker of table is tested
From the data in above-mentioned table 1 can be seen that the sulphur calcium silicate types phosphorus sulphoaluminate cement clinker for preparing of the present invention with
Common sulphate aluminium cement is compared, and has (the non-Mixed With Admixture of embodiments above, in practical application of faster setting time
A certain amount of retarder, which can be added, to carry out its setting time the control of science, and will not be caused to significantly affect to intensity), more
Strong early strength and later strength increase.Statistics indicate that this cement corrosion resistance of chloride ion ability is stronger in table 2, this is because phosphorus
The introducing of aluminate, phosphorus calcium aluminate is instead of part calcium sulphoaluminate, and after secondary clacining, sulphur calcium silicates replaces C2S realizes phosphorus aluminium
Sour calcium, calcium sulphoaluminate, sulphur calcium silicates and four kinds of essential minerals of calcium aluminoferrite coexist.In addition, it can be seen that the present invention 28 in table 2
After its maintenance, there is more excellent scour ＆ wear resistance energy, the reason is that containing more iron glue after aquation of the present invention, impart this water
The good resistant to sea water performance of flushing of mud, can be used for rapid rush-repair and the maintenance of ocean engineering.
Claims (4)
1. a kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker, which is characterized in that its raw material chemical content percentage forms such as
Under：CaO 40~50%, Al2O325~35%, Fe2O34~6%, SiO25~8%, SO38~11%, P2O51.5~
2.3%, ZnO 0.8~1%.
2. sulphur calcium silicate types phosphorus sulphoaluminate cement clinker according to claim 1, which is characterized in that its clinker
Mineral composition includes：10~15% phosphorus calcium aluminates, 20~35% sulphur calcium silicates, C4A3$ 30~45%, C4AF 10~20% and 2
~10% interphase.
3. a kind of preparation method of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker described in claim 1, which is characterized in that it
Include the following steps：
A) weighing dispensing is carried out by composition of raw materials, carries out first time calcining after mixing, and keep the temperature 1-2h；
B) by after the semi-finished product clinker grinding obtained by step a), incorporation is equivalent to the gypsum of semi-finished product clinker quality 6~11%, then
Secondary low temperature calcination is carried out, sulphur calcium silicate types phosphorus sulphate aluminium cement is obtained after keeping the temperature 1-2h.
4. the preparation method of sulphur calcium silicate types phosphorus sulphate aluminium cement according to claim 3, which is characterized in that for the first time
Calcination temperature is 1360~1380 DEG C, and second of calcination temperature is 1150~1200 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810069431.1A CN108314344B (en) | 2018-01-24 | 2018-01-24 | Calcium sulfosilicate type phospho-sulphoaluminate cement clinker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810069431.1A CN108314344B (en) | 2018-01-24 | 2018-01-24 | Calcium sulfosilicate type phospho-sulphoaluminate cement clinker |
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| Publication Number | Publication Date |
|---|---|
| CN108314344A true CN108314344A (en) | 2018-07-24 |
| CN108314344B CN108314344B (en) | 2020-09-08 |
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| CN201810069431.1A Active CN108314344B (en) | 2018-01-24 | 2018-01-24 | Calcium sulfosilicate type phospho-sulphoaluminate cement clinker |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078393A (en) * | 2019-05-15 | 2019-08-02 | 盐城工学院 | A kind of method of low temperature preparation sulphur calcium silicates-sulphate aluminium cement |
| 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 |
| CN113149492A (en) * | 2021-04-14 | 2021-07-23 | 济南大学 | Q-phase-containing phospho-sulphoaluminate cement and preparation method thereof |
| CN113200690A (en) * | 2021-04-22 | 2021-08-03 | 济南大学 | Modified sulphoaluminate cement containing Q phase and preparation method thereof |
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| JPS55167162A (en) * | 1979-06-08 | 1980-12-26 | Nihon Cement | Manufacture of concrete product |
| CN1498870A (en) * | 2002-11-08 | 2004-05-26 | 胡佳山 | Gelatinization material of phosphoaluminic salt system |
| CN104140216A (en) * | 2014-06-24 | 2014-11-12 | 济南大学 | High-iron phosphoaluminate cement clinker |
| CN104609750A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Sulphoaluminate cement and preparation method thereof |
| CN105669062A (en) * | 2014-11-22 | 2016-06-15 | 黄石永明环保科技有限公司 | Phosphoaluminate early strength cement clinker being high in content of calcium aluminoferrite |
| CN107021654A (en) * | 2017-05-31 | 2017-08-08 | 重庆大学 | A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof |
-
2018
- 2018-01-24 CN CN201810069431.1A patent/CN108314344B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55167162A (en) * | 1979-06-08 | 1980-12-26 | Nihon Cement | Manufacture of concrete product |
| CN1498870A (en) * | 2002-11-08 | 2004-05-26 | 胡佳山 | Gelatinization material of phosphoaluminic salt system |
| CN104140216A (en) * | 2014-06-24 | 2014-11-12 | 济南大学 | High-iron phosphoaluminate cement clinker |
| CN105669062A (en) * | 2014-11-22 | 2016-06-15 | 黄石永明环保科技有限公司 | Phosphoaluminate early strength cement clinker being high in content of calcium aluminoferrite |
| CN104609750A (en) * | 2015-02-09 | 2015-05-13 | 重庆大学 | Sulphoaluminate cement and preparation method thereof |
| CN107021654A (en) * | 2017-05-31 | 2017-08-08 | 重庆大学 | A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078393A (en) * | 2019-05-15 | 2019-08-02 | 盐城工学院 | A kind of method of low temperature preparation sulphur calcium silicates-sulphate aluminium cement |
| CN110078393B (en) * | 2019-05-15 | 2022-01-11 | 盐城工学院 | Method for preparing calcium sulfosilicate-sulphoaluminate cement at low temperature |
| 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 |
| CN113149492A (en) * | 2021-04-14 | 2021-07-23 | 济南大学 | Q-phase-containing phospho-sulphoaluminate cement and preparation method thereof |
| CN113200690A (en) * | 2021-04-22 | 2021-08-03 | 济南大学 | Modified sulphoaluminate cement containing Q phase and preparation method thereof |
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| CN108314344B (en) | 2020-09-08 |
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