CN104402270B - A kind of high calcium fly-ash cement and preparation method thereof - Google Patents
A kind of high calcium fly-ash cement and preparation method thereof Download PDFInfo
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- CN104402270B CN104402270B CN201410711210.1A CN201410711210A CN104402270B CN 104402270 B CN104402270 B CN 104402270B CN 201410711210 A CN201410711210 A CN 201410711210A CN 104402270 B CN104402270 B CN 104402270B
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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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Abstract
The invention discloses a kind of high calcium fly-ash cement and preparation method thereof, containing the composition of following mass percent: Portland clinker 30 ~ 50%；High-calcium fly ass 40 ~ 60%；Desulfurated plaster 3.1 ~ 3.3%；Silicon ash 4.8 ~ 5.0%；Waterglass 1.0 ~ 1.1%；Composite exciting agent 0.7 ~ 1.0%；Wherein, described composite exciting agent is the mixture of triethanolamine and sodium sulfate.The present invention provides a kind of large amount high-calcium fly ash cement, improves utilization of fly ash rate, it is possible to reduce the consumption of Portland clinker, and utilize industrial by-product desulfurated plaster and silicon ash is raw material simultaneously, meets again the process of industrial residue and recycles.
Description
Technical field
The invention belongs to building material technical field, be specifically related to a kind of high calcium fly-ash cement and preparation method thereof.
Background technology
Flyash is the grain dust that coal dust is collected after boiler combustion, and its generation amount accounts for the 1/4 of Coal-fired capacity.The fast development of power industry makes the yield of thermal power plant flyash be continuously increased, statistics display, and within 2013, Coal Ash in China yield reaches 5.3 hundred million tons, compares 1 year and increases by 2.31%.Flyash has become as the main source of China's solid waste.Storing up in a large number of flyash not only can take a large amount of soil, and can cause serious environmental pollution.Therefore, it is achieved the large-scale comprehensive of flyash utilizes, turn waste into wealth the problem becoming extremely urgent.
Flyash mainly by silicon oxide, aluminium oxide, calcium oxide, ferrum oxide, unburnt charcoal and on a small quantity other oxide formed, its material composition mainly have glass phase, amorphous phase and crystalline mineral phase three major types.Wherein, glass phase and amorphous phase content are relatively big, and crystallization mainly has mullite, quartz, Anhydrite etc..Flyash has a chemical composition similar to cement, has again pozzolanic activity simultaneously, and utilizing coal ash for manufacturing is to realize one of approach that flyash utilizes on a large scale for cement.At present, domestic having produced substantial amounts of Portland fly ash cement, the flyash mixed is the ordinary fly ash that calcium oxide content is relatively low mostly, and its activity index is relatively low.Meanwhile, the addition content of flyash is only limitted between 20%～30% so that the overall utilization of flyash is relatively low.Therefore, development powder coal ash utilizes technology imperative in the large-scale comprehensive of cement industry.
High-calcium fly ass refers to the flyash that calcium oxide content is more than 10%, containing substantial amounts of rich calcium, rich iron glass body and more calcium oxide crystalline solid.Compared with ordinary fly ash, high-calcium fly ass has that water requirement is little, loss on ignition is low, fineness is thin, activity index advantages of higher.Therefore, high-calcium fly ass replace ordinary fly ash become cement industry main ash source become trend.But high-calcium fly ass contains higher free calcium oxide simultaneously, improper use likely can bring the consequence that cement (concrete) stability is bad, it is necessary to control effectively it.Therefore, the volume of current high-calcium fly ass is relatively low, it is proposed that volume general control, within 30%, the most still fails to be applied on a large scale.In order to realize the high-calcium fly ass extensive utilization in cement industry, it is necessary for solving volume stability that large amount high-calcium fly ash (>=40%) causes due to free calcium oxide and volume increases the problem causing strength of cement to reduce.
Summary of the invention
The technical problem to be solved in the present invention is the volume stability problem that in large amount high-calcium fly ash (>=40%), free calcium oxide causes and the problem causing strength of cement to reduce owing to addition content increases.
In order to solve above-mentioned technical problem, the present invention provides a kind of large amount high-calcium fly ash cement.The high calcium fly-ash cement of the present invention, make use of substantial amounts of industrial by-products, and with the addition of additive and composite exciting agent, thus high-calcium fly ass is carried out mechanical and chemical activation process and can clear up the free calcium oxide in flyash, thus solve the volume stability problem that free calcium oxide causes, ensure that pulverized fuel ash cement has higher intensity simultaneously；Finally realize high-calcium fly ass large dosage in cement and utilize (addition content >=40%), obtain a kind of large amount high-calcium fly ash cement.
Concrete, the high calcium fly-ash cement of the present invention, containing the composition of following mass percent:
Portland clinker 30 ~ 50%；
High-calcium fly ass 40 ~ 60%；
Desulfurated plaster 3.1 ~ 3.3%；
Silicon ash 4.8 ~ 5.0%；
Waterglass 1.0 ~ 1.1%；
Composite exciting agent 0.7 ~ 1.0%；
Wherein, described composite exciting agent is the mixture of triethanolamine and sodium sulfate.
Preferably, in described composite exciting agent, the mass ratio of triethanolamine and sodium sulfate is 1:3.
Preferably, mass percent >=15% shared by CaO in described high-calcium fly ass.It is further preferred that granularity 400 mesh screen residue of described high-calcium fly ass is not more than 10%.
Preferably, described silicon ash is metallurgy industry by-product tail ash, wherein SiO2Shared mass percent is >=90%.
Preferably, described desulfurated plaster is the industry byproduct of coal-burning power plant's gained, wherein CaSO4Shared mass percent is >=90%.Wherein, the preparation method of described desulfurated plaster is: obtain by-product desulfurated plaster in coal-burning power plant, by by-product desulfurated plaster heat treatment 1 ~ 3h under 100 ~ 120 ° of C, to dry.
The preparation method of the large amount high-calcium fly ash cement that the present invention provides is employing grinding, prepares without calcine technology, specifically comprises the following steps that
By Portland clinker and desulfurated plaster first mixing and ball milling 1-3 hour in roller ball mill of suitable proportion, Control granularity 300 mesh screen residue is not more than 10%；Be subsequently adding a certain proportion of high-calcium fly ass, silicon ash, waterglass, composite exciting agent carry out mix grinding again and excite activation processing to prepare large amount high-calcium fly ash cement in 2 hours.
The positive effect of the present invention is:
1, the present invention provides a kind of large amount high-calcium fly ash cement, improves utilization of fly ash rate, it is possible to reduce the consumption of Portland clinker, and utilize industrial by-product desulfurated plaster and silicon ash is raw material simultaneously, meets again the process of industrial residue and recycles.
2, compared with prior art, the large amount high-calcium fly ash cement prepared by the present invention need not calcine technology, decreases energy consumption, only excites process by mechanochemistry, it is possible to realizes high-calcium fly ass large dosage in cement and utilizes.Its addition content (mass ratio) is that 28 days comprcssive strength of the pulverized fuel ash cement of 60% gained remain to meet 42.5 strength grade standards.Use the present invention, be possible not only to energy efficient, reduce clinker dosage, and also reduce cement cost, the cement produced by the present invention, can be widely used in building field.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, so that those skilled in the art can be better understood from the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
A kind of high calcium fly-ash cement that the present invention provides, containing the composition of following mass percent:
Portland clinker 30 ~ 50%；
High-calcium fly ass 40 ~ 60%；
Desulfurated plaster 3.1 ~ 3.3%；
Silicon ash 4.8 ~ 5.0%；
Waterglass 1.0 ~ 1.1%；
Composite exciting agent 0.7 ~ 1.0%；
Wherein, composite exciting agent is the mixture of triethanolamine and sodium sulfate.
The preparation method of the high calcium fly-ash cement of the present invention, comprises the steps:
1) ball milling: by Portland clinker and desulfurated plaster mixing and ball milling, obtain mixture；
2) mechanochemistry excites process: the mixture that step 1) obtains carries out mixing and ball milling again with high-calcium fly ass, silicon ash, waterglass and composite exciting agent, it is thus achieved that high calcium fly-ash cement.
Each component of high calcium fly-ash cement of the present invention can carry out mechanical and chemical activation process by ball milling, clears up the free calcium oxide in flyash, thus solves the volume stability problem that free calcium oxide causes.Wherein composite exciting agent (triethanolamine and the mixture of sodium sulfate) can efficiently excite mechanical and chemical activation to process under ball milling condition, and silicon ash and waterglass further assist promotion composite exciting agent effect.Due to these additives and the addition of composite exciting agent (desulfurated plaster, silicon ash, waterglass) so that the present invention only excites process by mechanochemistry, it is possible to realizes high-calcium fly ass large dosage in cement and utilizes, without calcine technology, decreases energy consumption；And owing to silicon ash particle is thin, activity is high, it is possible to increase the early strength of cement.
With embodiment, the present invention will be described below
Chemical composition of PCA used in embodiments of the invention is as shown in table 1, and the more flyash of high oxidation calcium content is equally applicable to the high calcium fly-ash cement of the present invention, and granularity 400 mesh screen residue of this high-calcium fly ass is not more than 10%.
Table 1 high-calcium fly ass chemical composition
Silicon ash used in embodiment is metallurgy industry by-product tail ash, after testing, wherein SiO2Shared mass percent is 92.8 %.Desulfurated plaster is the industry byproduct of coal-burning power plant's gained, after testing, and wherein CaSO4Shared mass percent is 92.1%.
Embodiment 1
The percentage by weight composition of the high calcium fly-ash cement of the present embodiment is as follows:
Portland clinker 50%；
High-calcium fly ass 40%；
Desulfurated plaster 3.3%；
Silicon ash 5.0%；
Waterglass 1.0%；
Composite exciting agent (triethanolamine and the sodium sulfate quality mixture than 1:3) 0.7%.
Preparation method is: 1) ball milling: first clinker and desulfurated plaster are carried out in tumbling ball mill ball milling 3h, and Control granularity 300 mesh screen residue is not more than 10%；2) mechanochemistry excites process: then high-calcium fly ass, silicon ash, waterglass, composite exciting agent is added together and carries out ball milling 2h in ball mill, it is thus achieved that high calcium fly-ash cement.
The strength of cement prepared the present embodiment according to the method for GB/T17671-1999 is tested, and result is as shown in table 2, it is known that the high calcium fly-ash cement of the present embodiment gained reaches the standard-required of 42.5 strength grades in GB175-2007.Further, through inspection experiment show, the high calcium fly-ash cement of the present embodiment through water of coal ash earth rubber sand examination recuperate protect 28 days after volume without cracking.
Embodiment 2
The percentage by weight composition of the high calcium fly-ash cement of the present embodiment is as follows:
Portland clinker 40%；
High-calcium fly ass 50%；
Desulfurated plaster 3.2%；
Silicon ash 4.9%；
Waterglass 1.0%；
Composite exciting agent (triethanolamine and the sodium sulfate quality mixture than 1:3) 0.9%.
Preparation method is: 1) ball milling: first clinker and desulfurated plaster are carried out in tumbling ball mill ball milling 2h, and Control granularity 300 mesh screen residue is not more than 10%；2) mechanochemistry excites process: then high-calcium fly ass, silicon ash, waterglass, composite exciting agent is added together and carries out ball milling 2h in ball mill, it is thus achieved that high calcium fly-ash cement.
The strength of cement prepared the present embodiment according to the method for GB/T17671-1999 is tested, and result is as shown in table 2, it is known that the high calcium fly-ash cement of the present embodiment 2 gained reaches the standard-required of 42.5 strength grades in GB175-2007.Further, through inspection experiment show, the high calcium fly-ash cement of the present embodiment through water of coal ash earth rubber sand examination recuperate protect 28 days after volume without cracking.
Embodiment 3
The percentage by weight composition of the high calcium fly-ash cement of the present embodiment is as follows:
Portland clinker 30%；
High-calcium fly ass 60%；
Desulfurated plaster 3.1%；
Silicon ash 4.8%；
Waterglass 1.1%；
Composite exciting agent (triethanolamine and the sodium sulfate quality mixture than 1:3) 1.0%.
Preparation method is: 1) ball milling: first clinker and desulfurated plaster are carried out in tumbling ball mill ball milling 2h, and Control granularity 300 mesh screen residue is not more than 10%；2) mechanochemistry excites process: then high-calcium fly ass, silicon ash, waterglass, composite exciting agent is added together and carries out ball milling 2h in ball mill, it is thus achieved that high calcium fly-ash cement.
The strength of cement prepared the present embodiment according to the method for GB/T17671-1999 is tested, and result is as shown in table 2, it is known that the high calcium fly-ash cement of the present embodiment 3 gained reaches the standard-required of 42.5 strength grades in GB175-2007.Further, through inspection experiment show, the high calcium fly-ash cement of the present embodiment through water of coal ash earth rubber sand examination recuperate protect 28 days after volume without cracking.
The bending and compressive strength of table 2 each embodiment gained large amount high-calcium fly ash cement
Showing from above-mentioned test, embodiment 3 utilizes the grog of 30%, the high-calcium fly ass of 60% to add additive and the composite exciting agent of total amount 10%, still can prepare the high calcium fly-ash cement of 42.5 labels.Substantially increase industrial by-products flyash utilization rate in cement.
The method using the present invention, can make high-calcium fly ass be utilized in a large number, still ensures that cement has qualified performance during addition content up to 60%, meet the Portland fly ash cement standard of 42.5 strength grades in GB175-2007 in the case of being not added with calcining.
Embodiment described above is only the preferred embodiment lifted by absolutely proving the present invention, and protection scope of the present invention is not limited to this.The equivalent that those skilled in the art are made on the basis of the present invention substitutes or conversion, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (9)
1. a high calcium fly-ash cement, it is characterised in that be made up of the composition of following mass percent:
Portland clinker 30 ~ 50%；
High-calcium fly ass 40 ~ 60%；
Desulfurated plaster 3.1 ~ 3.3%；
Silicon ash 4.8 ~ 5.0%；
Waterglass 1.0 ~ 1.1%；
Composite exciting agent 0.7 ~ 1.0%；
Wherein, described composite exciting agent is the mixture of triethanolamine and sodium sulfate, and in described composite exciting agent, the mass ratio of triethanolamine and sodium sulfate is 1:3.
High calcium fly-ash cement the most according to claim 1, it is characterised in that mass percent >=15% shared by CaO in described high-calcium fly ass.
High calcium fly-ash cement the most according to claim 2, it is characterised in that granularity 400 mesh screen residue of described high-calcium fly ass is not more than 10%.
High calcium fly-ash cement the most according to claim 1, it is characterised in that described silicon ash is metallurgy industry by-product tail ash, wherein SiO2Shared mass percent is >=90%.
High calcium fly-ash cement the most according to claim 1, it is characterised in that described desulfurated plaster is the industry byproduct of coal-burning power plant's gained, wherein CaSO4Shared mass percent is >=90%.
High calcium fly-ash cement the most according to claim 1, it is characterised in that the preparation method of described desulfurated plaster is: obtain by-product desulfurated plaster in coal-burning power plant, by by-product desulfurated plaster heat treatment 1 ~ 3h under 100 ~ 120 ° of C, to dry.
7. the preparation method of the high calcium fly-ash cement described in any one of claim 1 ~ 6, it is characterised in that comprise the steps:
1) by Portland clinker and desulfurated plaster mixing and ball milling, mixture is obtained；
2) mixture that step 1) obtains carries out mixing and ball milling again with high-calcium fly ass, silicon ash, waterglass and composite exciting agent, it is thus achieved that high calcium fly-ash cement.
Preparation method the most according to claim 7, it is characterised in that step 1) Ball-milling Time is 1 ~ 3 hour, granularity 300 mesh screen residue of gained mixture is not more than 10%.
Preparation method the most according to claim 7, it is characterised in that step 2) Ball-milling Time is 1 ~ 3 hour.
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| CN104876459B (en) * | 2015-05-15 | 2017-03-15 | 中南大学 | A kind of flyash activity exciting agent and large amount high-calcium fly ash cement |
| CN106866062B (en) * | 2015-12-11 | 2019-04-23 | 北京市湟砂建材科技有限公司 | Finishing cement of the organo-mineral complexing of high-content fly ash and its preparation method and application |
| JP6278147B1 (en) * | 2017-04-28 | 2018-02-14 | 住友大阪セメント株式会社 | Mixed cement |
| EP3807230A4 (en) * | 2018-06-15 | 2022-03-30 | Sarod Greenback LLP | Engineered concrete binder composition comprising mechano-chemically modified component and method of producing the same |
| CN109912243B (en) * | 2019-03-19 | 2020-04-10 | 西卓子山草原水泥集团包头三固有限责任公司 | Cement produced by utilizing industrial solid wastes |
| CN111233352B (en) * | 2019-12-13 | 2022-03-18 | 南京理工大学 | Method for preparing active mixed material by using material containing tobermorite phase |
| CN113336459A (en) * | 2020-09-14 | 2021-09-03 | 辰溪县宏兴新材料科技有限公司 | Ultrahigh-toughness high-mixing-amount pulverized coal cement-based composite material and preparation method thereof |
| CN114804748A (en) * | 2022-04-24 | 2022-07-29 | 陕西正诚路桥工程研究院有限公司 | High-calcium fly ash/cement composite cementing material solidified clay and preparation method thereof |
| CN116003001B (en) * | 2023-02-22 | 2023-10-24 | 上海百奥恒新材料有限公司 | Mine filling cement and preparation method and application thereof |
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| CN1154952A (en) * | 1996-01-15 | 1997-07-23 | 王永逵 | High-performance concrete special-use auxiliary material |
| CN101117005A (en) * | 2007-09-04 | 2008-02-06 | 中国林业科学研究院木材工业研究所 | Cement flakeboard and production process thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154952A (en) * | 1996-01-15 | 1997-07-23 | 王永逵 | High-performance concrete special-use auxiliary material |
| CN101117005A (en) * | 2007-09-04 | 2008-02-06 | 中国林业科学研究院木材工业研究所 | Cement flakeboard and production process thereof |
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