CN113149492A - Q-phase-containing phospho-sulphoaluminate cement and preparation method thereof - Google Patents
Q-phase-containing phospho-sulphoaluminate cement and preparation method thereof Download PDFInfo
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- CN113149492A CN113149492A CN202110399620.7A CN202110399620A CN113149492A CN 113149492 A CN113149492 A CN 113149492A CN 202110399620 A CN202110399620 A CN 202110399620A CN 113149492 A CN113149492 A CN 113149492A
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- 239000004568 cement Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 9
- 230000036571 hydration Effects 0.000 abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 102100033772 Complement C4-A Human genes 0.000 abstract 1
- 101000710884 Homo sapiens Complement C4-A Proteins 0.000 abstract 1
- 150000004645 aluminates Chemical class 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000001506 calcium phosphate Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 5
- 229940078499 tricalcium phosphate Drugs 0.000 description 5
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 5
- 235000019731 tricalcium phosphate Nutrition 0.000 description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- RJMZIUFNDNYWDU-UHFFFAOYSA-N 3-chloro-2-hydroxy-5-phenylbenzoic acid Chemical compound ClC1=C(O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1 RJMZIUFNDNYWDU-UHFFFAOYSA-N 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- -1 phosphosulphate aluminate Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000010959 steel Substances 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
- 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/02—Phosphate cements
- C04B12/025—Phosphates of ammonium or of the alkali or alkaline earth metals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明涉及一种含Q相的磷硫铝酸盐水泥及其制备方法，属于胶凝材料的技术领域。该水泥熟料由Q相‑硫铝酸钙(C4A3$)‑磷硫铝酸钙(CPSA)‑硅酸二钙(C2S)‑铁铝酸四钙(C4AF)五种矿相组成。本发明能够在富铁环境下较低温度实现C4A3$、Q相、C4AF和C8A6P共存，既引入了水化活性高的C8A6P和Q相，又有效降低体系中C2AS的生成，能够大幅改善熟料体系的水化强度，相比于硫铝酸盐水泥有着更低的烧成温度，且具有良好的早期和长期力学性能。The invention relates to a Q-phase-containing phosphorosulfoaluminate cement and a preparation method thereof, belonging to the technical field of cementitious materials. The cement clinker is composed of Q-phase - calcium sulfoaluminate ( C4A3 $ )-calcium phosphosulfoaluminate (CPSA) -dicalcium silicate (C2S)-tetracalcium ferric aluminate (C4AF) five Mineral phase composition. The invention can realize the coexistence of C 4 A 3 $, Q phase, C 4 AF and C 8 A 6 P at lower temperature in an iron-rich environment, not only introducing C 8 A 6 P and Q phase with high hydration activity, but also Effectively reducing the generation of C 2 AS in the system can greatly improve the hydration strength of the clinker system, has a lower firing temperature than sulfoaluminate cement, and has good early and long-term mechanical properties.
Description
Technical Field
The invention relates to a Q-phase-containing phosphosulphate aluminate cement and a preparation method thereof, belonging to the technical field of cementing materials.
Background
In the last 70 th century, the national institute of building materials invented sulphoaluminate cement, the hydration product of which is calcium sulphoaluminate (C)4A3Calcium silicate (C)2S) is taken as a main component,the early hydration reaction speed is high, and the product has the characteristics of quick hardening and early strength and good durability such as high impermeability, frost resistance, corrosion resistance and the like. Compared with common Portland cement, the sulphoaluminate cement has lower sintering temperature and less carbon emission, and is high-performance cement with low energy consumption and environmental protection. However, in practical application, the defects that the growth strength is slow in the middle and later periods, the shrinkage occurs after long-term use and the like are found. To this end, researchers have attempted to introduce simultaneously two minerals with intermediate and late strength development, calcium phosphoaluminate (C), in a sulfoaluminate, aluminous cement clinker system8A6P) and Q phases to improve the later strength thereof. But C in the novel clinker system4A3Phase $ Q, $ C4AF and C8A6The forming temperatures of the four mineral phases P are different, a large amount of mineral phases are difficult to form in the same temperature range, and meanwhile, the gehlenite with low hydration activity is easy to appear in a complex system.
Disclosure of Invention
Aiming at the problems, the invention provides the Q-phase-containing phosphosulfoaluminate cement which can realize C at a lower temperature in an iron-rich environment4A3Phase $ Q, $ C4AF and C8A6P coexists, and the invention has the advantages that C with high hydration activity is introduced8A6P and Q phases, and effectively reduce C in the system2The generation of AS can greatly improve the hydration strength of a clinker system, has lower sintering temperature compared with sulphoaluminate cement, and has good early and long-term mechanical properties.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a Q-phase-containing phospho-sulphoaluminate cement, the cement clinker is composed of Q-phase-calcium sulphoaluminate (C)4A3Calcium Phosphosulphoaluminate (CPSA) -dicalcium silicate (C)2S) -Tetracalcium aluminoferrite (C)4AF) five mineral phases.
Further, the mineral composition of the cement clinker is specifically as follows:
phase Q: 10 to 30 percent;
C4A3$：30-60%；
CPSA：15-30%；
C2S：5-15%；
C4AF：5-10%。
the invention also provides a preparation method of the Q-phase-containing phosphosulfoaluminate cement clinker, which comprises the following steps: calculating and weighing raw materials according to the mineral proportion, and sieving by a standard sieve to obtain 6-10% of screen residue; then stirring by a ball mill, drying and preparing a sample; and (3) putting the sample into a low-temperature oven for drying, then putting the sample into a high-temperature resistance furnace for calcining, taking out the sample and then quenching to obtain the cement clinker.
Further, the particle size of the standard sieve is 200 meshes.
Further, the calcination process is carried out at 1330 ℃ for 2 h.
The invention has the beneficial effects that: the invention can realize C at lower temperature in iron-rich environment4A3Phase $ Q, $ C4AF and C8A6P coexists, namely C with high hydration activity is introduced8A6P and Q phases, and effectively reduce C in the system2The generation of AS can greatly improve the hydration strength of a clinker system, has lower sintering temperature compared with sulphoaluminate cement, and has good early and long-term mechanical properties.
Detailed Description
The technical solution of the present invention is further explained and illustrated by the following specific embodiments.
The raw materials that this experiment adopted are laboratory analysis pure reagent, specifically include: tricalcium phosphate, calcium carbonate, calcium sulfate, iron oxide, alumina, titanium dioxide, and basic magnesium carbonate.
Example 1
The raw material comprises the following components in percentage by weight:
tricalcium phosphate: 29.2 percent
Calcium carbonate: 21.8 percent
Calcium sulfate: 18.2 percent of
Iron oxide: 4.4 percent
Alumina: 19.6 percent
Titanium dioxide: 2.5 percent
Basic magnesium carbonate: 4.3 percent of
Example 2
The raw material comprises the following components in percentage by weight:
tricalcium phosphate: 33.2 percent
Calcium carbonate: 20.8 percent of
Calcium sulfate: 16.7 percent
Iron oxide: 4.2 percent of
Alumina: 18.9 percent
Titanium dioxide: 2.2 percent of
Basic magnesium carbonate: 4.0 percent
Example 3
The raw material comprises the following components in percentage by weight:
tricalcium phosphate: 35.2 percent of
Calcium carbonate: 20.3 percent of
Calcium sulfate: 17.4 percent
Iron oxide: 3.0 percent
Alumina: 17.8 percent
Titanium dioxide: 2.5 percent
Basic magnesium carbonate: 3.8 percent of
Comparative example 1
The raw material comprises the following components in percentage by weight:
tricalcium phosphate: 30.2 percent
Calcium carbonate: 23.1 percent
Calcium sulfate: 18.7 percent
Iron oxide: 4.9 percent
Alumina: 20.1 percent of
Titanium dioxide: 3.0 percent
In examples 1-3 and comparative example 1, 200g of raw materials are calculated and weighed according to the mineral proportion, the particle size is that the raw materials pass through a standard sieve of 200 meshes, and the residue on sieve is 6-10%. And then stirring by using a ball mill, drying and preparing a sample. The sample is 3X 1.5X 0.2cm3And (3) putting the cuboid block into a low-temperature oven for drying, then putting the cuboid block into a high-temperature resistance furnace for calcining, keeping the temperature for 2 hours at 1330 ℃, taking out and quenching to obtain the cement clinker. The clinker and the steel ball are put into a ball milling tank to be milled to a certain fineness and are sieved by a 200-mesh sieve, and the residue on the sieve is controlled to be 0.2-0.5%. The mold is 2X 2cm3And (3) forming, wherein the water-cement ratio is 0.35, curing in a room-temperature curing chamber for 24h, demolding, putting the samples of each example and each comparative example into a curing box, curing for 3d, 7d and 28d respectively under the standard conditions of constant temperature and constant humidity, and then respectively carrying out compressive strength test, wherein the specific results are shown in table 1.
TABLE 1
Claims (5)
1. A Q-phase containing phospho-sulphoaluminate cement is characterized in that the cement clinker is prepared from Q-phase calcium sulphoaluminate (C)4A3Calcium Phosphosulphoaluminate (CPSA) -dicalcium silicate (C)2S) -Tetracalcium aluminoferrite (C)4AF) five mineral phases.
2. The Q-phase containing phosphosulfoaluminate cement of claim 1, wherein the mineral composition of the cement clinker is specifically:
phase Q: 10 to 30 percent;
C4A3$：30-60%；
CPSA：15-30%；
C2S：5-15%；
C4AF：5-10%。
3. a process for the preparation of a Q-phase containing phosphosulfoaluminate cement clinker according to claim 1 or 2, characterized in that it comprises the following steps: calculating and weighing raw materials according to the mineral proportion, and sieving by a standard sieve to obtain 6-10% of screen residue; then stirring by a ball mill, drying and preparing a sample; and (3) putting the sample into a low-temperature oven for drying, then putting the sample into a high-temperature resistance furnace for calcining, taking out the sample and then quenching to obtain the cement clinker.
4. The method of claim 3, wherein the standard sieve has a particle size of 200 mesh.
5. The method of claim 3 or 4, wherein the calcination process is performed at 1330 ℃ for 2 h.
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| CN202110399620.7A CN113149492B (en) | 2021-04-14 | 2021-04-14 | Q-phase-containing phospho-sulphoaluminate cement and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110399620.7A CN113149492B (en) | 2021-04-14 | 2021-04-14 | Q-phase-containing phospho-sulphoaluminate cement and preparation method thereof |
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| CN113149492A true CN113149492A (en) | 2021-07-23 |
| CN113149492B CN113149492B (en) | 2023-02-07 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246496A (en) * | 1991-08-15 | 1993-09-21 | Associated Universities, Inc. | Phosphate-bonded calcium aluminate cements |
| CN1600727A (en) * | 2004-10-22 | 2005-03-30 | 济南大学 | A kind of aluminate cement material containing Q phase mineral |
| CN106082724A (en) * | 2016-06-08 | 2016-11-09 | 武汉理工大学 | The strongest a kind of high, high resistance to corrosion portland cement and preparation method thereof |
| CN107986655A (en) * | 2017-12-25 | 2018-05-04 | 济南大学 | A kind of phosphor aluminate cement is modified sulphoaluminate cement clinker |
| CN108059377A (en) * | 2017-12-25 | 2018-05-22 | 济南大学 | A kind of C4A3The phosphoaluminate clinker of $ types |
| CN108314344A (en) * | 2018-01-24 | 2018-07-24 | 济南大学 | A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker |
-
2021
- 2021-04-14 CN CN202110399620.7A patent/CN113149492B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246496A (en) * | 1991-08-15 | 1993-09-21 | Associated Universities, Inc. | Phosphate-bonded calcium aluminate cements |
| CN1600727A (en) * | 2004-10-22 | 2005-03-30 | 济南大学 | A kind of aluminate cement material containing Q phase mineral |
| CN106082724A (en) * | 2016-06-08 | 2016-11-09 | 武汉理工大学 | The strongest a kind of high, high resistance to corrosion portland cement and preparation method thereof |
| CN107986655A (en) * | 2017-12-25 | 2018-05-04 | 济南大学 | A kind of phosphor aluminate cement is modified sulphoaluminate cement clinker |
| CN108059377A (en) * | 2017-12-25 | 2018-05-22 | 济南大学 | A kind of C4A3The phosphoaluminate clinker of $ types |
| CN108314344A (en) * | 2018-01-24 | 2018-07-24 | 济南大学 | A kind of sulphur calcium silicate types phosphorus sulphoaluminate cement clinker |
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| CN113149492B (en) | 2023-02-07 |
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