CN102936104B - Method for preparing rapid hardening high-early-strength cement clinker - Google Patents
Method for preparing rapid hardening high-early-strength cement clinker Download PDFInfo
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- CN102936104B CN102936104B CN201210424696.1A CN201210424696A CN102936104B CN 102936104 B CN102936104 B CN 102936104B CN 201210424696 A CN201210424696 A CN 201210424696A CN 102936104 B CN102936104 B CN 102936104B
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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
Abstract
The invention provides a method for preparing rapid hardening high-early-strength cement clinker. Limestone, monohydrallite milltailings, ordinary coal ash and gypsum serve as raw amterials, rapid hardening high-early-strength Belite sulphate aluminium cement clinker is calcined at the temperatures of 1350+/-20 DEG C, the clinker comprises, by weight, 50-52% of C2S, 28-30% of C4A3S and 16-18% of C4AF and a small quantity of amorphous phase substances. According to the method, most of the used aluminous materials are monohydrallite milltailings which are industrial residues which are discharged by aluminium factories, the initial setting time of the obtained clinker is less than 5 minutes, more than 30MPa of the strength of 6 hours can be achieved, and at the same time, the 28d strength of the clinker can reach about 55 MPa.
Description
Technical field
The present invention relates to the cement material of building material field, particularly a kind of method of preparing high-early-strength belite sulphoaluminate cement clinker.
Background technology
China's bauxite resource is compared with horn of plenty, but the overwhelming majority belongs to diaspore type, and more than 80% bauxite aluminium-silicon, than between 5～8, can not adopt external conventional bayer process to produce aluminum oxide.According to the practical situation of China's aluminum oxide mineral resource, low grade ore resource in reasonably utilizing, China scientific worker has proposed " ore dressing one producing aluminium oxide by bayer " new technology route, and progressively promote in each Chinalco of China, become the topmost production technique of current China alumina industry.Adopt this new production technique, need to China generally in low-grade bauxite carry out ore dressing, produce the dressing-works of 500,000 tons of concentrate per year and want the milltailings of ten thousand tons of the nearly l3 of output, therefore produced a large amount of milltailings waste residues for one.On the one hand, these milltailings are stored up the series of problems such as can bring contaminate environment, account for firming; On the other hand, also contain a large amount of useful resources in bauxite, alumina content is higher, is a kind of secondary resource with very great development utility value.These milltailings are carried out to effective resource utilization exploitation, not only can greatly alleviate their pollutions to environment, the more important thing is by the use value of further these available resources of excavation, thereby can use to greatest extent resource, economize on resources, meet the desirability of recycling economy development.
Belite aluminosulfate cement, owing to having less energy-consumption, low-carbon emission, high performance advantage simultaneously, becomes the focus of current international cement circle research, has obtained in recent years significant achievement in research.Mei Ta (Mehta) professor of the U.S. had had once researched and developed and had consisted of: 45% C2S, 20%
15% C4AF(tetracalcium aluminoferrite), 20%
the cement of (dehydrated gyp-), has also obtained patent, and this cement has obtained in test good performance.Internationally recognizable manufacture of cement business Lafarge SA (lafarge), has also also carried out large quantity research to belite aluminosulfate cement in recent years, applied for 5-25%C2AF,
40-75%C2S is the patent of the high belite sulphoaluminate cement clinker of chief component, and in order to ensure the performance of cement, they add some trace elements as additive in the time of clinker burning, and part C2S is existed with à form.China Sinoma International Engineering Co., Ltd., Tianjin Branch, by a large amount of testing laboratories, half industrialization and industrialization research, recently study successfully the active belite aluminosulfate cement taking aluminous fly-ash as main alumina based material, applied for à type C2S, the 28-40% of β type C2S, 25-30% that mineral composition is 25-30%
the active belite sulphoaluminate cement clinker patent of the C4AF of 4-12%.By special mineral composition design and coupling, obtain performance and approach and be better than the High Quality Clinker of ordinary Portland cement, the in very large range use field of substituted for silicon acid salt cement.The successful exploitation of belite aluminosulfate cement, produces for energy-saving and cost-reducing, the low-carbon (LC) of Cement industry, has not only brought new development opportunity, and will produce far-reaching influence.Except the advantage of the aspect such as less energy-consumption, low-carbon emission, another considerable advantage of belite aluminosulfate cement various industrial residues of can dissolving in large quantities exactly, the aluminum oxide that bauxite is rich in, can be as the aluminum raw material of belite sulphoaluminate cement clinker, for development belite aluminosulfate cement, expand its raw material scope of application and all there is vital role.
No matter be the recycling exploitation aspect from bauxite gangue, or further abundant and improve aspect from belite aluminosulfate cement range of product, utilize bauxite calcining high-early-strength belite sulphoaluminate cement clinker, all there is positive development meaning.Along with the fast development of China's industry, a large amount of industrial residues of generation lie on the table or store up, and not only serious environment pollution also causes the waste of resource, utilize these industrial residues to prepare the potentiality of novel concrete material very large, of far-reaching significance.
Summary of the invention
The object of the invention is to, by optimizing mineral composition and the coupling of cement clinker, control and reduce the impact of the harmful elements such as potassium in bauxite, sodium, provide one to there is fast hard and powerful feature early, and later strength can reach the preparation method of the belite sulphoaluminate cement clinker of 52.5 grade ordinary Portland cement levels.
The present invention adopts technical scheme to be: a kind of method of preparing rapid hardening and early strength cement grog, use the bauxite of 22-26%, the ordinary fly ash of 10-12%, the Wingdale of 50-54%, the gypsum of 12-14%, make raw material according to ordinary method, at the temperature of 1350 ± 20 DEG C, be fired into a kind of belite sulphoaluminate cement clinker.This grog, due to the iron phase eutectic (C4AF) of high-content and potassium, the sodium trace element of Optimum Contents, produces the characteristic of high-early-strength, is less than 5 minutes time of coagulation, and within 6 hours, intensity can be greater than 30MPa.Clinker mineral composition is mainly: the C2S of 50-52%; 28-30%'s
the C4AF of 16%-18%, and a small amount of amorphous phase material.
The preparation method that the present invention proposes, comprises following concrete steps:
1) take raw material according to following weight percent: the bauxite of 22-26%, the ordinary fly ash of 10-12%, the Wingdale of 50-54%, the plaster stone lime stone of 12-14%.
2) raw material preparation: the raw material according to preset blending ratio is mixed, dried, the levigate weight percent for 8-12%(that tails over to 80 μ m sieves in milling equipment), obtain raw meal powder.
3) calcining: by the raw meal powder obtaining, in the temperature range of 1330-1370 DEG C, ensureing that calcination environment is all the time under oxidizing atmosphere, calcining at constant temperature 40-60 minute, until all mineral can both be completed into, makes grog.
In the mineral processing tailing of bauxite that the present invention uses, the content of the trace element such as iron oxide content and potassium, sodium is all high than other alumina-bearing material, fully, reasonably utilizes this feature, makes the cement clinker making have the feature of high-early-strength.High iron oxide content, makes can form in clinker mineral the iron phase eutectic (C4AF) of a greater number, this mineral aquation speed, and early strength is higher.The more complicated of impact of the trace element such as potassium, sodium.These elements too high levels in grog, easily causes cement clinker performance degradation, and low strength even produces retraction phenomenon.The degree having a negative impact for reducing the elements such as potassium in bauxite, sodium, when batching, adopt ordinary fly ash part to replace the measure of bauxite, control the two and reach suitable ratio, just the disadvantageous effect of the element such as potassium, sodium in grog can be reduced to minimum degree.The potassium, the sodium element that keep Optimum Contents in grog, melt in some clinker minerals it altogether, contributes on the contrary to improve the hydration activity of clinker mineral, and the characteristic that produces high-early-strength for grog has vital role.By the Combinatorial Optimization to clinker mineral, and calcination condition is constantly perfect, the final grog obtaining, be less than 5 minutes time of coagulation, within 6 hours, intensity is greater than 30MPa, and later strength also can reach 55MPa left and right, is equivalent to the level of 52.5 grade ordinary Portland cements.
The invention has the beneficial effects as follows: a kind of industrial residue-bauxite that utilizes aluminium manufacturer to discharge, aid in other material, made a kind of cement clinker with premium properties, this cement clinker has the characteristic of high-early-strength, has sufficiently high later strength guarantee simultaneously.This cement, in the special engineerings such as rapid construction, repairing rush construction, has a good application prospect.The present invention not only can thoroughly solve the recycling problem of the bauxite of aluminium manufacturer's discharge, and this industrial residue of dissolving in a large number and thoroughly, has also made a kind of novel concrete grog with less energy-consumption, low carbon dioxide emission.The development of this novel concrete is energy-saving and cost-reducing for Cement industry, and low-carbon (LC) is produced and environment protection aspect all has positive meaning.Therefore, economic and social benefit of the present invention is remarkable, has a extensive future.
Embodiment
The invention provides a kind of method of preparing rapid hardening and early strength cement grog.First, by weight percent be: the Wingdale of 50-54%, the bauxite of 22-26%, the ordinary fly ash of 10-12%, the gypsum of 12-14%, broken, mixedly respectively mix according to predetermined proportion after dry, levigate to the tailing over as 8-12% of 80 μ m square hole sieves in grinding machine, obtain cement slurry.Raw meal powder is added to 1% tap water, stirring and putting into internal diameter is 8cm, in the circular grinding tool of dark 2cm, utilizes baby press to be pressed into material cake, puts into testing furnace at the temperature lower calcination 50-60 minute of 1330-1370 DEG C after oven dry.Or directly raw meal powder is fed in half industrialization kiln, control the flow velocity of raw material in kiln, make material at the thermal zone stop 40-50 minute of 1330-1370 DEG C, guarantee has enough ventilations and oxidizing atmosphere in kiln simultaneously, avoids the decomposition of gypsum in kiln to cause the loss of element sulphur.The clinker mineral composition obtaining after calcining is: the C2S of 28-30%, 28-30%'s
the C4AF of 16-18%, and a small amount of amorphous phase material.
Below in conjunction with specific embodiment, the present invention is described in further detail:
Embodiment 1:
1) selection of raw material
Use the raw material with following (in table 1) four kinds of chemical compositions.
The chemical composition of four kinds of raw materials of table 1
| LOSS | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | TiO 2 | K 2O | Na 2O | SO 3 | |
| Wingdale 1 | 43.66 | 0.50 | 0.20 | 0.14 | 54.20 | 1.10 | 0.00 | 0.10 | 0.20 | 0.03 |
| Bauxite gangue 1 | 10.43 | 27.13 | 44.04 | 12.06 | 0.80 | 0.76 | 2.02 | 2.41 | 0.37 | 0.62 |
| Flyash 1 | 5.10 | 53.78 | 27.46 | 5.76 | 4.83 | 2.02 | 0.59 | 0.30 | 0.11 | 0.28 |
| Gypsum 1 | 3.69 | 2.24 | 0.69 | 0.58 | 38.76 | 0.26 | 0.00 | 0.13 | 0.11 | 53.38 |
2) taking of raw material
According to clinker mineral design requirements, consist of according to weight percent: 54.0% Wingdale, 22.0% bauxite, 12% ordinary fly ash, 12.0% gypsum, take the 2.7kg Wingdale 1 through broken, the bauxite 1 of 1.1kg, the ordinary fly ash 1 of 0.6kg, the gypsum 1 of 0.6kg mixes.
3) raw material preparation and moulding
By the 5.0kg raw material mixing, levigate to the tailing over as 8-12% of 80 μ m square hole sieves in pulverizer, make raw meal powder.Add 1% tap water at raw meal powder, stirring and putting into internal diameter is 8cm, in the circular grinding tool of dark 2cm, utilizes baby press to be pressed into material cake, will expect cake oven dry at 100 DEG C in baking oven.
4) calcining of grog
Get 8-10 piece material cake at every turn, put into and be warmed up in advance the testing furnace of 1330 DEG C and calcine 60 minutes, until all material cakes all burn down.Grog after calcining utilizes fan blast-cold to room temperature, approximately can obtain the grog of 3.5kg.
5) composition of clinker mineral
Will be after overcooled chamotte crushing, utilize the fineness of ball mill grinding to specific surface area 400 ± 50 ㎡/kg.The clinker mineral composition that utilizes the quantitative analysis method of XRD diffraction to measure is shown in Table 2.
The mineral composition of table 2 grog
| Clinker mineral | C2S | C4A3S | C4AF | Amorphous phase material |
| Content, % | 52.1 | 27.9 | 18.2 | 1.8 |
6) physicals of grog
According to standard GB17671-1999 and GB/T1346-2001, the intensity to cement clinker and consumptive use of water normal consistence, and time of coagulation etc. physicals measurement result see shown in 3.
The physicals of table 3 grog
Embodiment 2:
1) selection of raw material
Use the raw material with following (in table 4) four kinds of chemical compositions.
The chemical composition of four kinds of raw materials of table 4
| LOSS | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | TiO 2 | K 2O | Na 2O | SO 3 | |
| Wingdale 2 | 41.72 | 3.54 | 0.73 | 0.41 | 52.74 | 0.51 | 0.00 | 0.09 | 0.02 | 0.02 |
| Bauxite gangue 2 | 11.98 | 26.58 | 43.98 | 11.50 | 0.98 | 0.69 | 2.20 | 1.33 | 0.11 | 0.12 |
| Flyash 2 | 0.38 | 54.76 | 24.90 | 7.23 | 5.36 | 2.30 | 0.95 | 1.84 | 1.26 | 0.30 |
| Gypsum 2 | 20.19 | 4.08 | 1.34 | 0.66 | 30.55 | 1.62 | 0.00 | 0.26 | 0.13 | 40.94 |
2) taking of raw material
According to clinker mineral design requirements, consist of according to weight percent: 50.0% Wingdale, 26.0% bauxite, 10% ordinary fly ash, 14.0% gypsum, take the 250kg Wingdale 2 through broken, the bauxite 2 of 130kg, the ordinary fly ash 2 of 50kg, the gypsum 2 of 70kg mixes.
3) raw material preparation and moulding
By the 500kg raw material mixing, levigate to the tailing over as 8-12% of 80 μ m square hole sieves in this industrialization grinding machine, make raw meal powder.
4) calcining of grog
Directly raw meal powder is fed in half industrialization kiln, control suitable feeding capacity and material flow, ensureing has enough ventilations and oxidizing atmosphere in kiln, make material at the thermal zone stop 40-5 minute of 1330-1370 DEG C, until clinker mineral all forms, the grog burning till utilizes single cylinder cooling machine to be cooled to room temperature.
5) composition of clinker mineral
Will be after overcooled chamotte crushing, utilize the fineness of ball mill grinding to specific surface area 400 ± 50 ㎡/kg.The clinker mineral composition that utilizes the quantitative analysis method of XRD diffraction to measure is shown in Table 5.
The mineral composition of table 5 grog
| Clinker mineral | C2S | C4A3S | C4AF | Amorphous phase material |
| Content, % | 50.2 | 29.9 | 16.1 | 3.8 |
6) physicals of grog
According to standard GB17671-1999 and GB/T1346-2001, the intensity to cement clinker and consumptive use of water normal consistence, and time of coagulation etc. physicals measurement result see shown in 6.
The physicals of table 6 grog
Content of the present invention is not limited in the above-described embodiment, and the technician in same area can propose easily other embodiment within technical director's thought of the present invention, but this embodiment should comprise within the scope of the invention.
Claims (2)
1. prepare the method for rapid hardening and early strength cement grog for one kind, it is characterized in that, use the bauxite of 22-26%, the flyash of 10-12%, the Wingdale of 50-54%, the gypsum of 12-14%, makes raw material, at the temperature of 1350 ± 20 DEG C, being fired into the presetting period is less than 5 minutes, and 6 hours intensity are greater than the high-early-strength belite sulphoaluminate cement clinker of 30MPa; The mineral composition of described cement clinker is: the C2S of 50.2-52.1%; 27.9-29.9%'s
; The C4AF of 16.1%-18.2%; The amorphous phase material of 1.8-3.8%.
2. the method for preparing rapid hardening and early strength cement grog according to claim 1, is characterized in that, Al in described bauxite
2o
3content>=40%, Fe
2o
3>=10%; Al in flyash
2o
3content≤30%.
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| CN104310820B (en) * | 2014-10-10 | 2016-08-17 | 北京工业大学 | A kind of method utilizing five yuan of mineral facies systems to prepare sulphoaluminate cement clinker |
| CN104478240A (en) * | 2014-11-25 | 2015-04-01 | 广西鱼峰水泥股份有限公司 | Process for improving mixing amount of mining ore-dressing scrap waste rocks in cement |
| CN104478239A (en) * | 2014-11-25 | 2015-04-01 | 广西鱼峰水泥股份有限公司 | Process for improving doping amount of mining and mineral separation scraps and waste stones in P.C32.5 cement |
| CN105060745B (en) * | 2015-08-14 | 2017-11-21 | 盐城工学院 | Belite aluminium sulfate ferrous aluminate cement and preparation method thereof |
| CN105753341B (en) * | 2016-02-26 | 2017-08-29 | 西南石油大学 | A kind of preparation method of calcium aluminoferrite |
| CN115159872A (en) * | 2022-08-12 | 2022-10-11 | 福建省矿投环保科技有限公司 | Method for preparing cementing material by using copper slag, bauxite tailings and coal gangue |
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| CN101023043A (en) * | 2004-07-20 | 2007-08-22 | 拉法尔热公司 | High belite-containing sulphoaluminous clinker, method for the production and the use thereof for preparing hydraulic binders |
| CN101302082A (en) * | 2008-04-30 | 2008-11-12 | 同济大学 | Low-alkali sulpho-aluminate cement calcined by using refuse incineration flyash and preparation thereof |
| CN102584045A (en) * | 2012-02-01 | 2012-07-18 | 天津中材工程研究中心有限公司 | Active belite-sulphate aluminum cement clinker and preparation method for active belite-sulphate aluminum cement clinker |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101023043A (en) * | 2004-07-20 | 2007-08-22 | 拉法尔热公司 | High belite-containing sulphoaluminous clinker, method for the production and the use thereof for preparing hydraulic binders |
| CN101302082A (en) * | 2008-04-30 | 2008-11-12 | 同济大学 | Low-alkali sulpho-aluminate cement calcined by using refuse incineration flyash and preparation thereof |
| CN102584045A (en) * | 2012-02-01 | 2012-07-18 | 天津中材工程研究中心有限公司 | Active belite-sulphate aluminum cement clinker and preparation method for active belite-sulphate aluminum cement clinker |
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