CN105330182A - White fast-setting, fast-hardening and high-belite sulphoaluminate cement clinker, and application and production technology thereof - Google Patents
White fast-setting, fast-hardening and high-belite sulphoaluminate cement clinker, and application and production technology thereof Download PDFInfo
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Abstract
The invention relates to a white fast-setting, fast-hardening and high-belite sulphoaluminate cement clinker, and also relates to an application and a production technology thereof. The mineral component of the cement clinker comprises 0.5-4.6% of f-CaO; the chemical component of the cement clinker comprises 12.9-16.1wt% of SiO2, 12-19wt% of Al2O3, 0.15-1.0wt% of Fe2O3, 49-53wt% of CaO and 12-18.5wt% of SO3; and the clinker rate range Cm is 1.01-1.137, and P is 0.62-1.44. The clinker is produced through calcining 30-50wt% of limestone, 26-46wt% of slag powder and 21.1-40wt% of desulfurized gypsum in a rotary kiln at 1250-1350DEG C. 26-97% Of the clinker, 3-19% of anhydrite and 0-55% of the slag powder, or 5-25% of the clinker, 14.4-19.0% of the anhydrite and 55.8-79% of the slag powder are mixed and ground to form white fast-setting, fast-hardening and high-belite sulphoaluminate cement and high-late strength and high-belite sulphoaluminate cement.
Description
Technical field
The invention belongs to building material field, relate to the improvement to quick setting and rapid hardening high belite aluminosulfate cement Industrialized processing technique.Specifically, be a kind of new variety white quick setting and rapid hardening high belite sulphoaluminate cement clinker, application and production technique thereof.
Background technology
Current building materials field is all greatly improved viewed from consumption and technical level to the application demand of white cement.Produce white cement and starting material are required that natively standard is high, complex process, energy consumption are large, blowdown is serious.The high-quality raw material adapting to produce is fewer and feweri, and price is more and more higher.Form the contradiction in supply and demand.
Mineral composition and the production technique of conventional white silicate cement are similar to ordinary Portland cement, and the key distinction is very strict to ingredient requirement.Raw materials should reduce the oxide content of the coloring elements such as Fe, Mn, Ti, Cr as far as possible, and that particularly have the greatest impact to white cement whiteness is Fe
2o
3content.In raw material, Wingdale accounts for more than 80%, produces white portland cement ton cement clinker consumption raw material high, calcining temperature 1500-1550 DEG C, approximately high than ordinary portland cement clinker 100 DEG C; Higher than sulphoaluminate cement clinker 200 DEG C, there is the background that carbon emission is high.
Lower, easy to crack, the easy accumulation of salt in the surface soil of the general early strength of conventional white silicate cement.Be divided into 32.5 grades, 42.5 grades, 52.5 grades Three Estates according to GB, ultimate compression strength 3d be respectively 12.0,17.0,22.0MPa, 28d be respectively 32.5,42.5,52.5MPa; Folding strength 3d is respectively 3.0,3.5,4.0MPa, 28d be respectively 6.0,6.5,7.0MPa.Early strength is low, and especially 3d folding strength is lower, and when manufacturing decoration element, cracking phenomena is many, and spoilage is high.In application, the easy accumulation of salt in the surface soil, directly affects the attractive in appearance of white cement goods, and its condensation is slow, early strength is low, is the major cause of the accumulation of salt in the surface soil.
White aluminosulfate cement is the new variety developed in recent years." nonmetalliferous ore " magazine 1997NO.1 phase delivers Ningxia building materials institute Duan Qingkui, releases in the article of golden root, addresses in laboratory and utilizes Coaseries kaolin to manufacture experimently sulplo-aluminate type white cement.Proposing essential mineral moiety is anhydrous calcium sulphoaluminate and Dicalcium Phosphate (Feed Grade), does not provide concrete data, also do not provide cement proportion in literary composition.
Chinese building material research institute Li Guangming, Liu Changfa, Chen Mingfang about (" CaO-SiO
2one Al
2o
3one BaSO
4" research of belite white cement clinker forming process in system) (Chinese building material science and technology, Volume Four the 6th phase), the imagination of industrial raw material Wingdale, kaolin, barite preparation belite white cement is adopted in laboratory study.In this cement, BaS0
4be solid-solution in C on the one hand
2among S, on the other hand with the sulplo-aluminate phase 3CABaSO forming baric containing aluminium phase reaction
4.This grog can make the 325# belite white cement meeting secondary white standard.
At present, white cement is the special cement being mainly used in building decoration.Compared with natural decorating materials, white cement uses more convenient, and color is easy to regulate, and is convenient to machine-shaping and construction.Therefore, major industrial country, nearly all based on white cement, adds coloured pigment mixing and makes colored cement, for veneer coating, decoration mortar, finished concrete, colourcree brick, various veneer wallboard, artistic floors etc.
Improve white cement quick setting and rapid hardening and high-strength performance, to improve white cement decoration element production efficiency, reduce component production energy consumption and pollution; Particularly reduce white cement contract with dry rate, overcome the question meanings such as white cement goods easily split, the easy accumulation of salt in the surface soil very great.
Summary of the invention
The object of the present invention is to provide a kind of white cement product of brand-new component structure.Particularly there is quick setting and rapid hardening and later strength and have the high belite sulplo-aluminate white cement significantly promoted.The technique means adopted in the present invention be by means of in the achievement in research of the present inventor for cement clinker, the composition design at white cement clinker to C
4aF component content is strict controlled in less than 3.04%, has continued to use in component about f-CaO and f-CaSO
4corresponding proportion, realize the breakthrough to high belite sulplo-aluminate white cement product index.The multinomial technical indicators such as prepared white cement ultimate compression strength significantly promotes, whiteness is stable break through, and have filled up the market vacancy and have obtained energy-conservation, the sharp effect of giving up, reducing discharging simultaneously.
The technology used in the present invention measure is as follows:
(1) be first prepare the special white quick setting and rapid hardening high belite sulphoaluminate cement clinker of the present invention
Contained by this cement clinker, mineral composition comprises C
4a
3 , C
2s, CaSO
4, C
4aF, key is that contained by this cement clinker, mineral component comprises 0.5 ~ 4.6%f-CaO.
Above-mentioned grog is by the mineral composition of following weight percent: the C of 22.67 ~ 37.24%
4a
3 , the C of 37.02 ~ 46.21%
2s, the CaSO of 13.51 ~ 26.33%
4, the f-CaO of 0.5 ~ 4.6%, the C of 0.46 ~ 3.04%
4aF, surplus is for mixing mineralogical composition.
In above-mentioned grog, surplus mixes mineralogical composition≤7.71%.
In above-mentioned grog, surplus mixes mineralogical composition and comprises MgO or CaOTiO
2, or Na
2sO
3, or K
2sO
3, or two or more mixture wherein.
The chemical composition that described grog has as following weight percents forms: 12.9 ~ 16.1%SiO
2, 12 ~ 19%Al
2o
3, 0.15 ~ 1%Fe
2o
3, 49 ~ 53%CaO, 12 ~ 18.46%SO
3, surplus is hybrid chemistry composition; Clinker moduli scope Cm:1.01 ~ 1.137, P:0.62 ~ 1.44.
(2) preparation method of white quick setting and rapid hardening high belite sulphoaluminate cement clinker
Present method method comprises the following steps:
(1) prepare woollen: calculate required each raw material dosage according to proportioning according to claim 1, take Wingdale, 26 ~ 46% slag powders and 21.1 ~ 40% desulfurated plasters that mass percent is 30 ~ 50%;
(2) raw material are prefabricated: the raw material woollen of preparation in (1) being obtained regulation fineness through grinding, homogenizing;
(3) calcine: the raw material of step (2) gained are calcined in rotary kiln at 1300 ± 50 DEG C, obtains cement clinker.
In above-mentioned (1) preparation woollen, Wingdale component feedstock portions or be all alkaline residue or carbide slag or their two or more mixture replacing, the principle of required control is that in grog, CaO content must be equivalent to 49 ~ 53%.
In above-mentioned (1) preparation woollen, be partly or entirely bauxitic clay or bauxitic clay mine tailing or white clay or pyrophyllite or kaolin or clay or their two kinds and two or more mixture replacings in slag powders component, the principle of required control is Al in grog
2o
3content must be equivalent to 12 ~ 19%.
(3) white quick setting and rapid hardening high belite aluminosulfate cement
White quick setting and rapid hardening high belite aluminosulfate cement, comprises cement clinker, adjust coagulate, component of promoting the strong, fill auxiliary material component institute proportioning.Key is: select the cement clinker said in (), tune coagulates, compositional selecting anhydrite of promoting the strong, fill auxiliary material select slag powders, and according to following weight per-cent mixture, grind to form cement: white quick setting and rapid hardening high belite sulphoaluminate cement clinker 26% ~ 97%, anhydrite 3% ~ 19%, slag powders 0% ~ 55%.
According to above-mentioned weight percent mixture, grind to form the physical and chemical indexes after cement and be:
Presetting period: 13 ~ 32 minutes, final setting time: 18 ~ 45 minutes; 2 hours ultimate compression strength: 6 ~ 25.2Mpa, 28 days ultimate compression strength: 48.5 ~ 103.1Mpa, 28 days degree of free swelling: 0.10% ~ 0.16%, limited expansion rate: in water in 28 days rate of expansion, 0.007% ~ 0.090%, 21 days air-0.011% ~ 0.056%, Hunter whiteness is up to 75.1-83.2.
(4) production technique of white quick setting and rapid hardening high belite aluminosulfate cement
This technique comprises the following steps:
1. the preparation of raw material: take Wingdale, 21.1 ~ 40% desulfurated plasters and 26 ~ 46% slag powders that mass percent is 30 ~ 50%, through raw mill grinding, then selection by winnowing, homogenizing, must enter kiln raw material;
2. the preparation of grog: by step 1. gained enter kiln raw material through 1300 ± 50 DEG C of calcinings in rotary kiln, obtain cement clinker, contained mineral component comprises 0.5 ~ 4.6%f-CaO, 0.46 ~ 3.04%C
4aF;
3. the preparation of cement: according to cement design grade and whiteness requirement, proportional range with reference to grog 26% ~ 97%, anhydrite 3% ~ 19%, slag powders 0% ~ 55%% selects the concrete ratio of anhydrite, slag powders and cement clinker, carry out rectification through little mill experiment and determine final blending ratio, remix grinding is to specific surface area>=480m
2/ Kg, makes cement.
Above-mentioned step
cement preparation technology in, before combined grinding, add the Quilonum Retard of 0 ~ 0.3%.
Above-mentioned step
cement preparation technology in, before combined grinding, add 0 ~ 1.8% calcium hydroxide.
Above-mentioned steps
cement preparation technology in, before combined grinding, add 0 ~ 0.5% citric acid.
Five white quick setting and rapid hardening high belite aluminosulfate cements (a small amount of grog adds micro-properties-correcting agent)
When adopting that grog is 5% ~ 25%, anhydrite 14.4% ~ 19%, slag powders 55.8% ~ 79%, the cement physicochemical property index that formed be:
16 ~ 30 minutes presetting periods, final setting time 20 ~ 39 minutes, 28 days most high compressive strength: 60 ~ 86.0Mpa, 28 days degree of free swelling: 0.12% ~ 0.16%, 0.021% ~ 0.042%, 21 the Heavenly Stems aerial-0.010% ~ 0.015%, Hunter whiteness 78.6-86.3 in limited expansion rate 28 sky and water.
Corrosion-resistant coefficient >=1.4 of above-mentioned cement in 3% concentration sulphuric acid sodium, 3% sodium carbonate, 3% sodium chloride solution, the corrosion-resistant coefficient in 3% concentration sulphuric acid magnesium, 3% magnesium chloride solution is more than or equal to 1.0.
Technical problem solved by the invention is activity based on Clinker Composition and by f-CaO, C in hydration process
4a
3 , C
2s and CaSO
4mutually excite, and after the effect that strongly excites of the active principle that contains in the filler that adds, make the ultimate compression strength of final cement can reach the outstanding index of 2h25.2MPa, 7d61.7MPa, 28d103.1Mpa, Hunter whiteness reaches between 75 ~ 85.And high-strength, cracking resistance, the contour dominance of the anti-accumulation of salt in the surface soil of quick setting and rapid hardening high belite aluminosulfate cement can be given full play of.
The present invention compares with the corresponding technology of white portland cement of the prior art the advantage had:
, white portland cement raw meal proportioning adopts fat lime stone, also comprises agalmatolite or china clay or silica sand or fluorite.Desulfurated plaster in raw meal proportioning of the present invention and slag powders are industry byproduct, and annual generation is very large, is a kind of utilization of waste material.Replace raw material agalmatolite, china clay, silica sand, these natural Mineral resources of fluorite, expanded the use range of fat lime stone, white cement product Sustainable development involved in the present invention is guaranteed.
, C in white portland cement clinker
3s is high, calcining temperature 1500 ~ 1550 DEG C, approximately high than ordinary portland cement clinker 100 DEG C; Higher than sulphoaluminate cement clinker 200 DEG C, higher than the cement clinker in the present invention 250 DEG C (burning clinker of cement temperature of the present invention 1300 ± 50 DEG C).The present invention has the advantage of energy-saving and emission-reduction.The slag of high-temperature calcination is employed in a large number in raw meal proportioning, slag loss on ignition is extremely low, and containing about 40% CaO, reduce further the Wingdale amount of allocating into of fire loss volume in raw material, thus reduce a ton grog consumption raw material amount, reduce hear rate, reduce further exhaust gas emission, especially carbon emission, particularly sulfurous gas is close to zero release.
, about many consumption about 0.8 ton, the grogs of white portland cement one ton of producing suitable quality, ton cement consumption grog is high, causes carbon emission high, and ton cement consumption about 0.5 ton, grog in the present invention, ton cement consumption grog is few.
, just reach 12.0 ~ 22.0MPa by GB/T2015-2005 white portland cement standard ultimate compression strength 3d, folding strength 3d just reaches 3.0 ~ 4.0MPa, and early strength is low, and decoration element in the urgent need to very high early strength to enhance productivity.In the present invention, cement 2 hours ultimate compression strength can reach 25.2MPa, more taller than the ultimate compression strength of white portland cement 3d.
, lower, easy to crack, the easy accumulation of salt in the surface soil of the general early strength of white portland cement, have impact on the qualification rate of the attractive in appearance of white cement goods and product.Cement of the present invention has high hour intensity, extremely low shrinking percentage, substantially increases resistance to cleavage and the yield rate of product; And improve the degree of compactness of cement products with microdilatancy function and pass through to accelerate setting and harden, substantially increase and suppress accumulation of salt in the surface soil performance.
The present invention also has obvious advantage compared with the white aluminosulfate cement reported in existing document:
Report in existing document that white aluminosulfate cement can burn till grog in 1300 ~ 1350 DEG C of temperature ranges, the 325# belite white cement meeting secondary white standard can be made.All significantly different from the raw material adopted in the present invention, clinker mineral composition, rate value calculating principle; The former can only make 325# belite white cement, and cement 28d ultimate compression strength of the present invention can reach 103.1Mpa, and physical and chemical index is much better than 325#.
The technique means adopted in the present invention has following distinguishing feature, defines outstanding technical progress:
(1) about grog
Contained by cement clinker of the present invention, mineral component comprises 0.5 ~ 4.6%f-CaO, C
4aF controls 0.46 ~ 3.04%, makes the proportion value of sulphoaluminate cement clinker create breakthrough improvement.Thus define outstanding coagulating feature soon firmly, soon and the feature that later strength is high and shrinking percentage is little can be realized.Significantly improve the quality of white cement, extend its application category.
(2) about the preparation method of grog for contribution of the present invention
New theory and rate value proportionlity is have employed in the proportioning of grog; industrial residue, waste material can be adopted in a large number by work in-process; not only be conducive to the protection of ecotope and protect resource, and directly enhancing all technical of white cement, greatly reducing production cost simultaneously.
(3) proportioning of white quick setting and rapid hardening high belite aluminosulfate cement and technological process are the guarantees of novel white cement superior quality
In the present invention under the proportion technique of cement clinker and the prerequisite of Technology, then add that tune coagulates, component of promoting the strong, filler prepared, and can form the white cement product of various model and purposes through all mixed mill.
Adopt white cement grog of the present invention, be equipped with anhydrite and slag powders, just can produce 13 ~ 32 minutes presetting periods, final setting time 18 ~ 45 minutes, 28 days most high compressive strength: 103.1Mpa, 28 days degree of free swelling: 0.10 ~ 0.16%, the white cement of 0.007 ~ 0.090%, 21 the Heavenly Stems aerial-0.011% ~ 0.056% in limited expansion rate 28 sky and water.
The technological process that white cement is produced comprises following innovative point:
1. follow basic rate value principle in raw material to the preparation of grog and create essential change with tradition: contained mineral component comprises 0.5 ~ 4.6%f-CaO, 0.46 ~ 3.04%C
4aF;
broken away from the dependence to high-quality Mineral resources in the production of cement, achieving to give up is main environmental protection concept.Grog, anhydrite, slag powders proportioning can be chosen according to the adaptive prediction scheme adjustment of cement mark, whiteness index and little mill.Finally realize specific surface area>=480m
2the production of/kg cement.
Early strength and late strength production scene adjustable.Realize later stage height by properties-correcting agent and a small amount of grog and strengthen white high belite aluminosulfate cement.
In technique scheme of the present invention, designing a small amount of f-CaO in grog as a kind of mineral composition of necessity, is main, crucial strategic structural point.Existing theory is thought: in ordinary portland cement clinker, allows f-CaO to be no more than 1.5%, otherwise can cause soundness of cement potential threat to form more tricalcium silicate; In common sulphoaluminate cement clinker, the most high-content of f-CaO is no more than 0.2%, and too much f-CaO can affect the stability of process of setting, even causes anxious solidifying.Traditional theory then thinks that the existence of f-CaO is all unfavorable to performance in above two kinds of cement, and containing the f-CaO mineral of 0.5% ~ 4.6% in cement clinker of the present invention, far beyond theory forbidden zone and this existence that is confirmed in experiment is useful.First, the existence of enough free ca avoids and produce low activity mineral due to calcium deficiency in grog sintering procedure, as gehlenite (C
2aS); Secondly, a small amount of f-CaO can promote the aquation of anhydrous calcium sulphoaluminate at the hydrated cementitious initial stage, and early stage setting and harden is accelerated, and this and the effect of free calcium oxide in common sulfoaluminate clinker are consistent, not contradiction.Only there is a large amount of high reactivities in common sulfoaluminate clinker
, content is between 60% ~ 70%, and it is too fast that a small amount of f-CaO is just enough to that its hydrated cementitious is hardened, and loses flowability rapidly, even causes anxious solidifying.And in the present invention, in cement clinker mineral, to only have 22.7% ~ 37.2%
, the early C of epistasis energy extreme difference
2s, up to 37 ~ 46.2%, needs the promoter action of f-CaO mineral that the quick setting and rapid hardening performance of cement just can be made to meet application needs; On the other hand, f-CaO mineral a small amount of in cement clinker of the present invention are calcined under 1300 ± 50 DEG C of low temperature, crystal is tiny, short texture, activity are higher, the whole aquation of meeting in hydration process, especially a small amount of f-CaO mineral hydration reaction will be faster, so the volume that there is not the later stage is unstable and the bad problem of stability; Add the silicon and aluminum source such as slag powders or flyash material during cement grinding, improve grinding fineness, in hydration reaction, the Al provided in the f-CaO in cement clinker and slag powders, flyash
2o
3, Fe
2o
3, SiO
2and SO in former cement clinker
3with after SO in the gypsum that adds
3water generation reaction calcium sulphoaluminate, aluminium glue, hydrated calcium silicate gel, excite the activity of slag powders, flyash, improves the early strength of cement, absorbs the expansion that f-CaO brings; Through great number tested data, the cement adopting technique scheme to manufacture, shows that degree of free swelling fluctuation range is less; Limited expansion rate confined expansion value and confined shrinkage value drop little, this cement cubic deformation is very little, and cracking resistance anti-permeability performance is excellent.
The host one of of calcium sulfate as cement clinker uses by the present invention in the industrial production.In cement clinker, calcium sulfate mineral contain 12.9% ~ 26.3%.More CaSO
4the burn-ability of raw material can be improved, reduce sinter leaching temperature; CaSO
4at high temperature can exist with liquid state, add the amount of liquid phase of cement clinker under firing temperature, enhance the relative diffusion rates between each composition, make the chemical reaction of other mineral of formation grog more fast with thorough; Calcium sulfate itself aquation can form terra alba, also can setting and harden; Calcium sulfate also can continue to react with another essential mineral anhydrous calcium sulphoaluminate in grog and water and forms early stage main hydration products ettringite, and cement quick setting and rapid hardening performance is strengthened.
Adopt the cement series product that above-mentioned technique means is produced, without the need to any admixture of admixture in application, only code requirement metallization processes step is by above-mentioned cement clinker, tune coagulates, component of promoting the strong, and namely all mixed mill of filler can obtain the high performance white high belite aluminosulfate cement of various label.Due to controlling of production process process matures, the equipment adopted and solid sulphur process quilt prove environment protecting obviously, expend the energy and obviously reduce, add and can use the development that industrial residue is conducive to recycling economy and the social benefit reduced costs on a large scale, the major technological breakthrough that the invention belongs in this area is described.
Accompanying drawing explanation
Fig. 1 is the schema of white quick setting and rapid hardening high belite sulphoaluminate cement clinker, cement and production technique thereof.
In flow process in Fig. 1, the production of grog is for reference with the Wingdale of 30 ~ 50%, 26 ~ 46% slag powders and 21.1 ~ 40% desulfurated plasters, the mixture of cement and grinding: white quick setting and rapid hardening high belite aluminosulfate cement is with grog 26% ~ 97%, anhydrite 3% ~ 19%, slag powders 0% ~ 55% for reference, white late-enhancement type high belite aluminosulfate cement is for reference with grog 5% ~ 25%, anhydrite 14.4% ~ 19%, slag powders 55.8% ~ 79%.
Embodiment
Further illustrate below in conjunction with embodiment and the object of the invention is how to realize.
Embodiment 1 ~ embodiment 6 is raw material material side proportionings
1. the preparation of raw material: according to the raw material material side proportioning in table 2, take the Wingdale that chemical composition is as shown in table 1, put into raw mill grinding, enters in raw mill mill tail lift subsequently; Simultaneously according to the raw material material side proportioning in table 2, take chemical composition slag powders as shown in table 1 and desulfurated plaster, tail lift is ground to raw mill with the Wingdale synchronous transport after grinding, 3 kinds of mass transport are to powder separating machine subsequently, after the mixing of powder separating machine selection by winnowing, qualified raw material conveyor is to raw material homogenizing silo, and defective raw material are sent raw mill back to and continued grinding; Kiln raw material must be entered after homogenizing.
In this step, the qualified powder of granularity among slag powders, desulfurated plaster does not enter raw mill, after screening, directly enters powder separating machine, substantially increase every platform of raw grinding system, per time output, considerably reduce the wearing and tearing of power consumption, ball consumption and liner plate, and directly decrease Fe
2o
3mixed volume, promoter action is served to raising grog whiteness.
The chemical composition of table 1 raw material
The weight percent of each composition in raw material material side during table 2 white quick setting and rapid hardening high belite sulphoaluminate cement clinker makes
2. the preparation of grog: by step 1. gained raw material in precalciner kiln through 1300 ± 50 DEG C of calcinings, obtain cement clinker.Simultaneously owing to reducing amount of lime, reduce calcining temperature and reduce coal consumption, decrease carbon emission, achieve sulfurous gas zero release.
3. the preparation of cement: according to proportioning take anhydrite, slag powders and step 2. in the cement clinker of gained, combined grinding is to specific surface area>=480m
2/ Kg, makes cement.
Concrete technical process is see accompanying drawing 1.
According to physicalies such as its degree of mobilization of " aluminosulfate cement " GB20472-2006 inspection, consumptive use of water normal consistence (%), time of coagulation and bending and compressive strength.The physicals of gained grog is in table 3.
The physicals of the white cement clinker prepared by table 3 embodiment 1 ~ embodiment 6
The grog presetting period prepared as seen from the table is all less than 15min, and final setting time is all not more than 22min, and within early stage 2 hours, ultimate compression strength reaches 8.5 ~ 22.5Mpa, and have the character of quick setting and rapid hardening, ultimate compression strength and folding strength are all high than sulphoaluminate cement clinker.
Cement clinker physicals under embodiment 7 ~ 16 different chemical composition, mineralogical composition, ingredient rate value.
In the present invention, contained by white quick setting and rapid hardening high belite sulphoaluminate cement clinker, mineral composition comprises C
4a
3 , C
4aF, C
2s, CaSO
4, key is also to comprise 0.5 ~ 4.6%f-CaO in mineral component contained by this white high belite sulphoaluminate cement clinker.The mineral composition (wt%) of cement clinker in the present embodiment, chemical composition (wt%), batching p and Cm lead value and physicals, respectively in table 4, table 5 and table 6.
The mineral composition composition (%) of table 4 white quick setting and rapid hardening high belite sulphoaluminate cement clinker
The chemical composition (%) of table 5 white quick setting and rapid hardening high belite sulphoaluminate cement clinker
The physicals of table 6 white quick setting and rapid hardening high belite sulphoaluminate cement clinker
Cement clinker ultimate compression strength prepared in the present embodiment list reaches 2h:4.8 ~ 24.6MPa, 28d:44 ~ 79.0MPa, in the high belite sulphoaluminate cement clinker Research Literature of low aluminium height silicon composition, have no relevant report.
Embodiment 17 ~ 35 gives the concrete data about white quick setting and rapid hardening high belite aluminosulfate cement component, and lists the leading indicator in the technical trial report of this embodiment.Embodiment is the selected grog of grog as embodiment 17 ~ 35 cement of embodiment 7 in the physicals table 6 of white quick setting and rapid hardening high belite sulphoaluminate cement clinker, and according to cement products made by above-mentioned cement process for making.Wherein step 3. in add slag powders and anhydrite or their equivalent material, the various gypsum adopted and the chemical composition of mixing material are in table 7, and each embodiment cement proportion and physicals are in table 8.The touchstone of degree of free swelling to press in the aluminosulfate cement standard of GB20472-2,006 7.6, and the touchstone of limited expansion rate performs by " cement expansive material " GB23439-2009.
First half-table the 8-A of the data of white cement embodiment 17-35
Latter half-table the 8-B of the data of white cement embodiment 17-35
Further experiment proves that, in proportioning adjustment, attrition process, continue the ratio reducing cement clinker, the Early-age behavior of cement can be subject to certain impact, but the intensity in later stage does not only have negative impact, has greatly improved on the contrary.This shows the innovative significance shown in the present invention, also treats further excavation.Embodiment 36-44 is the selected grog of grog as embodiment 36 ~ 44 cement of embodiment 7 in the physicals table 6 of white quick setting and rapid hardening high belite sulphoaluminate cement clinker, and according to cement products made by above-mentioned cement process for making.
The first half of the implementation data of white cement embodiment 36-44--table 9-A
Latter half-Biao the 9-B of the implementation data of white cement embodiment 36-44
In above-described embodiment; anhydrite component can all or part of desulfurated plaster or natural dihydrate gypsum or semi-hydrated gypsum or phosphogypsum or fluorgypsum substitute; or with two or more mixture replacing of above-mentioned gypsum, the substitution principle of gypsum is the effect ensureing that the tune of equivalence coagulates, promotes the strong; Described slag powders can with Wingdale or rhombspar or sandstone or slag or dry powder or quartzite or talcum powder or flyash or their mixture be all or part of substitutes, the principle substituted is, the respective performances index reaching grade of cement standard must be ensured after substituting, preferential employing has lateral reactivity material, preferential employing pulverulent material, the white stopping composition of preferential employing, reduces Fe in grinding
2o
3incorporation, improve cement whiteness.Described one white quick setting and rapid hardening high belite aluminosulfate cement, can add 0 ~ 1.8% calcium hydroxide to shorten time of coagulation, improve early strength and late strength.The Quilonum Retard that can add 0 ~ 0.30% shortens time of coagulation, improves early strength, and the Quilonum Retard added can use lithium hydroxide, lithium chloride all or part of alternative; Described a kind of quick setting and rapid hardening high belite aluminosulfate cement, can add 0 ~ 0.5% citric acid and extend time of coagulation, improve late strength, the citric acid added, and available Trisodium Citrate, Sunmorl N 60S are all or part of to be substituted.
Embodiment 45
The cement that cement Example 30 is chosen in cement anti-corrosion test of the present invention does anti-corrosion test, test-results puts into solution after 7 days, operative norm in Table 10-A and all test-block standard curings of table 10-B: Rapid test for sulphate resistance of cement GB/T2420/1981; The sodium sulfate of concentration 3%, sodium carbonate, sodium-chlor three kinds of corrosion-resistant coefficients: be respectively 1.46,1.41,1.51; The corrosion-resistant coefficient of three kinds of cement in 3% concentration sulphuric acid magnesium, 3% magnesium chloride solution is all more than or equal to 1.0, and corrosion-resistant coefficient is high.
Table 10-A
Table 10-B
Claims (17)
1. a white quick setting and rapid hardening high belite sulphoaluminate cement clinker, contained mineral composition comprises C
4a
3 , C
2s, CaSO
4, C
4aF, is characterized in that contained by this cement clinker, mineral component comprises 0.5 ~ 4.6%f-CaO.
2., according to the said white quick setting and rapid hardening high belite sulphoaluminate cement clinker of claim 1, it is characterized in that the mineral composition of above-mentioned grog by following weight percent: the C of 22.67 ~ 37.24%
4a
3 , the C of 37.02 ~ 46.21%
2s, the CaSO of 13.51 ~ 26.33%
4, the f-CaO of 0.5 ~ 4.6%, the C of 0.46 ~ 3.04%
4aF, surplus is for mixing mineralogical composition.
3., according to the said white quick setting and rapid hardening high belite sulphoaluminate cement clinker of claim 2, it is characterized in that in above-mentioned grog, surplus mixes mineralogical composition≤7.71%.
4. the white quick setting and rapid hardening high belite sulphoaluminate cement clinker according to Claims 2 or 3, to is characterized in that in above-mentioned grog that surplus mixes mineralogical composition and comprises MgO or CaOTiO
2, or Na
2sO
3, or K
2sO
3, or two or more mixture wherein.
5. white quick setting and rapid hardening high belite sulphoaluminate cement clinker according to claim 2, is characterized in that the chemical composition that described grog has as following weight percents forms: 12.9 ~ 16.1%SiO
2, 12 ~ 19%Al
2o
3, 0.15 ~ 1%Fe
2o
3, 49 ~ 53%CaO, 12 ~ 18.46%SO
3, surplus is hybrid chemistry composition; Clinker moduli scope Cm:1.01 ~ 1.137, P:0.62 ~ 1.44.
6. a preparation method for white quick setting and rapid hardening high belite sulphoaluminate cement clinker, is characterized in that said method comprising the steps of:
(1) prepare woollen: calculate required each raw material dosage according to proportioning according to claim 1, take Wingdale, 26 ~ 46% slag powders and 21.1 ~ 40% desulfurated plasters that mass percent is 30 ~ 50%;
(2) raw material are prefabricated: the raw material woollen of preparation in (1) being obtained regulation fineness through grinding, homogenizing;
(3) calcine: the raw material of step (2) gained are calcined in rotary kiln at 1300 ± 50 DEG C, obtains cement clinker.
7. preparation method according to claim 6, it is characterized in that in described (1) preparation woollen, Wingdale component feedstock portions or be all alkaline residue or carbide slag or their two or more mixture replacing, the principle of required control is that in grog, CaO content must be equivalent to 49 ~ 53%.
8. preparation method according to claim 6, it is characterized in that in described (1) preparation woollen, be partly or entirely bauxitic clay or bauxitic clay mine tailing or white clay or pyrophyllite or kaolin or clay or their two kinds and two or more mixture replacings in slag powders component, the principle of required control is Al in grog
2o
3content must be equivalent to 12 ~ 19%.
9. preparation method according to claim 6, it is characterized in that described desulfurated plaster is partly or entirely natural dehydrated gyp-or natural dihydrate gypsum or semi-hydrated gypsum or phosphogypsum or Tai-Ace S 150 or two or more the mixture replacing that is rich in the industrial waste of gypsum component, the principle of required control is SO in grog
3it is SO in grog that content is equivalent to 12 ~ 18.46% required principles controlled
3content is equivalent to 12 ~ 18.46%.
10. a white quick setting and rapid hardening high belite aluminosulfate cement, comprise cement clinker, tune coagulates, component of promoting the strong, fill auxiliary material component institute proportioning, it is characterized in that: select the said cement clinker of claim 1, tune coagulates, compositional selecting anhydrite of promoting the strong, fill auxiliary material select slag powders, and according to following weight per-cent mixture, grind to form cement: white quick setting and rapid hardening high belite sulphoaluminate cement clinker 26% ~ 97%, anhydrite 3% ~ 19%, slag powders 0% ~ 55%.
11. white quick setting and rapid hardening high belite aluminosulfate cements according to claim 10, is characterized in that: according to above-mentioned weight percent mixture, grind to form cement physical and chemical indexes and be:
Presetting period: 13 ~ 32 minutes, final setting time: 18 ~ 45 minutes; 2 hours ultimate compression strength: 6 ~ 25.2Mpa, 28 days ultimate compression strength: 48.5 ~ 103.1Mpa, 28 days degree of free swelling: 0.10% ~ 0.16%, limited expansion rate: in water in 28 days rate of expansion, 0.007% ~ 0.090%, 21 days air-0.011% ~ 0.056%, Hunter whiteness 75.1-83.2.
The production technique of 12. 1 kinds of white quick setting and rapid hardening high belite aluminosulfate cements, is characterized in that specifically comprising the following steps:
1. the preparation of raw material: take Wingdale, 21.1 ~ 40% desulfurated plasters and 26 ~ 46% slag powders that mass percent is 30 ~ 50%, through raw mill grinding, then selection by winnowing, homogenizing, must enter kiln raw material;
2. the preparation of grog: by step 1. gained enter kiln raw material through 1300 ± 50 DEG C of calcinings in rotary kiln, obtain cement clinker, contained mineral component comprises 0.5 ~ 4.6%f-CaO, 0.46 ~ 3.04%C
4aF;
3. the preparation of cement: according to cement design grade and whiteness requirement, proportional range with reference to grog 26% ~ 97%, anhydrite 3% ~ 19%, slag powders 0% ~ 55% selects the concrete ratio of anhydrite, slag powders and cement clinker, carry out rectification through little mill experiment and determine final blending ratio, remix grinding is to specific surface area>=480m
2/ Kg, makes cement.
The production technique of 13. a kind of white quick setting and rapid hardening high belite aluminosulfate cements according to claim 12, is characterized in that described step
cement preparation in, before combined grinding, add the Quilonum Retard of 0 ~ 0.3%.
The production technique of 14. a kind of white quick setting and rapid hardening high belite aluminosulfate cements according to claim 12, is characterized in that described step
cement preparation in, before combined grinding, add 0 ~ 1.8% calcium hydroxide.
The production technique of 15. a kind of white quick setting and rapid hardening high belite aluminosulfate cements according to claim 12, is characterized in that described step
cement preparation in, before combined grinding, add 0 ~ 0.5% citric acid.
16. 1 kinds of white quick setting and rapid hardening high belite aluminosulfate cements, is characterized in that: have employed that grog described in claim 1 is 5% ~ 25%, anhydrite 14.4% ~ 19%, slag powders 55.8% ~ 79% and claim 13, claim 14, quantity described in claim 15;
16 ~ 30 minutes presetting periods, final setting time 20 ~ 39 minutes, 28 days most high compressive strength: 60 ~ 86.0Mpa, 28 days degree of free swelling: 0.12% ~ 0.16%, 0.021% ~ 0.042%, 21 the Heavenly Stems aerial-0.010% ~ 0.015%, Hunter whiteness 78.6-86.3 in limited expansion rate 28 sky and water.
17. according to the said white quick setting and rapid hardening high belite aluminosulfate cement of claim 16, it is characterized in that: corrosion-resistant coefficient >=1.4 of this cement in 3% concentration sulphuric acid sodium, 3% sodium carbonate, 3% sodium chloride solution, the corrosion-resistant coefficient in 3% concentration sulphuric acid magnesium, 3% magnesium chloride solution is more than or equal to 1.0.
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