CN1104388C

CN1104388C - Cement of mineral slugs with high amount of sulfate, cement of furnace slug and production of same

Info

Publication number: CN1104388C
Application number: CN95107331A
Authority: CN
Inventors: 益田义高
Original assignee: San Puyan
Current assignee: San Puyan
Priority date: 1994-12-26
Filing date: 1995-05-31
Publication date: 2003-04-02
Anticipated expiration: 2015-05-31
Also published as: JPH08175855A; CN1125698A

Abstract

The present invention discloses a method to inexpensively obtain the subject cement having excellent hardening properties, initial and long-term hardness, by blending a blast furnace granulated slag having a specific composition with coal ash, gypsum, Portland cement and an additive such as sodium sulfate in a fixed ratio. Then the mixture is blended with a small amount of an additive such as sodium sulfate, aluminum sulfate, sodium carbonate, sodium aluminate or sodium citrate in an outer ratio to give high sulfate slag cement/high early strength slag ash cement.

Description

High-sulfate slag cement and manufacture method thereof

The present invention relates to compound high-sulfate slag cement, the early strong slag ash cement that becomes high-alumina phase, the gypsum that will add by increase and decrease in addition and alkali-activator to improve the chemical constitution upgrading by blast furnace water quenching slag and coal ash, and manufacture method.

The Bora-zon reaction of the latent hydraulicity that utilizes blast furnace slag and coal ash is arranged in the prior art field, use gypsum and alkali-activator, perhaps mix high-sulfate slag cement, blast furnace cement and the fly ash cement that uses portland cement.

Supersulphated cement in the past, water and hot water, have the excellent tart of anti-sulphur reverse side, exist the setting and harden time long, early strength is little, the shortcoming of the surperficial generation deterioration of hardenite.Therefore, the inventor by using organic additive, has eliminated the practicalization that above-mentioned shortcoming has advanced domestic and international project as shown in the public clear 60-50738 communique of spy.

But as the factor that its rerum natura is produced a very large impact, there is following problem in the variation along with the blast furnace slag of raw material.

(1) existing system iron blast furnace operation process be according to each cause raw material condition, operating condition change, flux composition at China's blast furnace operation, with compare in the past because the moiety of having controlled aluminum oxide, calcium, blast-furnace slag than the lowland changes, aluminum oxide, calcium reduce, opposite magnesium oxide increases, and major ingredient is generally CaO 38-40%, Al ₂O ₃12-14% is following, MgO 5-5.5%, SiO ₂About 31-36%, with the Al in the slag composition that the generation of the ettringite of control high-sulfate slag cement intensity is associated ₂O ₃, CaO containing ratio, theoretical value descends in the reality.In addition, the % in this specification sheets is weight %.

Again, find the property and the proterties of condensing, reach target strength and stability thereof, have an obligato composition range of necessity from the intensity that causes the high-sulfate slag cement that real vitriol reacts.

In addition, obtain the composition of high strength and stability, in 3 compositions system, CaO50%, SiO ₂30%, Al ₂O ₃Near 20%, be considered to exist the field that obtains maximum intensity, CaO and Al ₂O ₃Minimizing, the minimizing of the heat that causes hardening, causing the deterioration of hardenite becomes the reason of having brought obstacle to certain product property management.

(2) increase and decrease the alkali-activator of interpolation a little from the cooperation scope that limits, intensity finds that property changes significantly, only just can obtain necessary strength in the field that limits.Therefore, the interpolation of alkali-activator follows the isocontour width of intensity minimum, during manufacturing and the qualitative control difficulty in when storage.

As the alkali-activator that adds, for example using portland cement, and under the cindery situation, best combined amount is 2-3%, has surpassed this scope, along with the increase of amount, intensity is found the property destabilization that becomes, the obvious deterioration of the property found.

(3) hardenite of relevant high-sulfate slag cement is in air set and in exposure, because carbon dioxide in air is soaked into diffusion by the surface, cause advancing of neutralisation fast, the flexural strength of surface deterioration and long-term material age is obviously low tendency, carbonatization countermeasure difficulty.

(4) the aforesaid hardenite poor durability freezing to melt, as its countermeasure air is present in the concrete with spumescence, but in the stable field of hardenite, import gas, it is low to cause proportionality intensity, therefore, unfavorable in the structured material use of the cold district that freezes easily, melts as structure usefulness.

When (5) hardenite of Ji Shuing had the situation of reinforcing bar, the invar material had corrosion-prone tendency, and tectum is essential thick.

Above-mentioned (1)-(5) are the problem points of high-sulfate slag cement essence.

So far in the known high-sulfate slag cement, satisfy to be fit to above-mentioned manufacture method the blast-furnace slag of obligato composition range be difficult to obtain, so hardenite also has the tendency of deterioration, embrittlement.

The objective of the invention is, since the past at the as a result gained data of practicality based on domestic and international projects, profoundly examine repeatedly, propose cheap high-sulfate slag cement, early strong slag coal ash cement with and manufacture method, and solve the problem points of above-mentioned (1)-(5).

That is to say, in the chemical ingredients by the byproduct blast furnace water quenching slag of making iron operation discharge, even CaO, Al ₂O ₃, SiO ₂The theoretical value destabilization of the main four-component of MgO, above-mentioned water granulated slag is as raw material, can be as the main raw material of producing cement, can obtain ideal high-sulfate slag cement, early strong slag coal ash cement, the byproduct coal ash that particularly has the blast furnace water quenching slag of latent hydraulicity and discharge from the fuel-burning power plant mixing, make its chemical consist of the high-alumina type, improve obligato constituent, enlarge the cooperation scope of alkali-activator, by the interaction between them, make the generation metamorphosis, the improvement of each proterties and high-intensity discovery may, have necessity that the strong early slag coal ash cement of high-sulfate slag cement of practicality does not burn till, and a water granulated slag, coal ash is cheap, expectation can reach cheap price, has realized the present invention.

According to one embodiment of the invention, first kind of strong early slag coal ash cement of high-sulfate slag cement contains SiO in constituent ₂31.00-36.00%, Al ₂O ₃12.30-14.47%, Fe ₂O ₃0.03-0.26%, CaO28.30-42.42%, SO ₃0.88-1.03%, MgO5.20-5.49%, MnO0.16-0.48%, TiO ₂0.46-0.82%, CaO/SO ₂Than for the blast furnace water quenching slag 40-80% of 1.6-1.36, from byproduct coal ash 3-20%, gypsum 4-35%, portland cement or the grog 2-40% of fuel-burning power plant discharge, add up to 100%, and add in addition therein more than at least a in minor amounts of additives sodium sulfate, Tai-Ace S 150, yellow soda ash, aluminic acid soda, the Trisodium Citrate etc., be the mixing fine powders end.

According to second embodiment of the invention, a kind of high-sulfate slag, early strong slag coal ash cement are provided, its coal ash contains SiO in constituent ₂34.18-55.06%, Al ₂O ₃17.81-30.59%, Fe ₂O ₃4.44-14.83%, CaO 0.66-14.7%, MgO 0.19-2.75%, SO ₃0.35-10.05%, R ₂O 1.66-4.80%, gypsum in constituent containing moisture+free water 0.04-0.23%, SiO ₂+ insoluble composition 2.00-3.00%, Al ₂O ₃+ Fe ₂O ₃2.00-2.30%, CaO40.00-42.00%, MgO0.11-2.00%, SO ₃The II type dehydrated gyp-of 50.00-55.50%, and constituent in contain constitution water 20.92-21.12%, SiO ₂+ insoluble composition 0.20-3.66%, Al ₂O ₃+ Fe ₂O ₃0.11-2.03%, CaO23.42-35.25%, MgO0.20-0.37%, SO ₃The dihydrate gypsum of 32.82-46.59% etc.

In the constituent that portland cement or grog contain, loss on ignition 0.3-0.8%, insoluble composition 0.01-0.10%, SiO ₂20.00-23.00%, Al ₂O ₃4.90-6.00%, Fe ₂O ₃2.00-4.00%, CaO62.00-66.00%, MgO1.00-3.00%, SO ₃1.00-2.50%, Na ₂O0.30-0.50%, K ₂O0.30-0.60%.

The 3rd kind of embodiment of the present invention provides the manufacture method of a kind of high-sulfate slag, early strong slag coal ash cement, contains SiO in the cement constituent ₂31.00-36.00%, Al ₂O ₃12.30-14.47%, Fe ₂O ₃0.03-0.26%, CaO28.30-42.4%, MgO5.20-5.49%, SO ₃0.88-1.03%, MnO0.16-0.48%, TiO ₂0.46-0.82%, CaO/SiO ₂Than for the blast furnace water quenching slag 40-80% (being preferably 50-60%) of 1.6-1.36 and

Contain SiO ₂34.18-55.06%, Al ₂O ₃17.81-30.59%, Fe ₂O ₃4.44-14.83%, CaO0.06-14.7%, MgO0.19-2.75%, SO ₃0.35-10.05%, R ₂The byproduct coal ash 3-20% (being preferably 4-14%) that discharges from the fuel-burning power plant of O1.66-4.80% and

Containing be moisture+free water 0.04-0.23%, SiO ₂+ insoluble composition 2.00-3.00%, Al ₂O ₃+ Fe ₂O ₃2.00-2.30%, CaO40.00-42.00%, MgO0.11-2.00%, SO ₃The II type dehydrated gyp-of 50.00-55.50% and contain constitution water 20.92-21.12%, SiO ₂+ insoluble composition 0.20-3.66%, Al ₂O ₃+ Fe ₂O ₃0.11-2.03%, SO ₃One or more gypsum 4-35% such as the dihydrate gypsum of 32.82-46.59% and

Contain loss on ignition 0.3-0.8%, insoluble composition 0.01-0.10%, SiO ₂20.00-23.00%, Al ₂O ₃4.90-6.00%, Fe ₂O ₃2.00-4.00%, CaO62.00-66.00%, MgO1.00-3.00%, SO ₃1.00-2.50%, Na ₂O 0.30-0.50%, K ₂The portland cement of O0.30-0.60% or grog 2-40% (being preferably 5-40%) amount to 100%,

Add in addition therein more than at least a 0.5-1.0% in sodium sulfate as additive, Tai-Ace S 150, yellow soda ash, aluminic acid soda, the Trisodium Citrate etc., mix to pulverize or pulverize and mix, surface area ratio is 4000cm ²/ g-6000cm ²/ g.

The another kind of method that the present invention's the 4th embodiment provides is, in the manufacture method of above-mentioned high-sulfate slag cement, gypsum has been to use II type dehydrated gyp-4-18% (being preferably 7-15%), in addition adds Tai-Ace S 150 0.5-5% or adds a kind of among sodium sulfate 0.5-5%, yellow soda ash 0.5-5%, sodium aluminate 0.5-5%, the Trisodium Citrate 0.5-5% simultaneously with it as additive.

The 5th embodiment of the present invention be in the 3rd embodiment morning strong slag coal ash cement manufacture method in, gypsum is to use dihydrate gypsum 4-35% (being preferably 6-10%), in addition adds sodium sulfate 0.5-5% as additive.

The strong early slag coal ash cement of the high-sulfate slag cement of first embodiment of the invention, shrend thing by the byproduct blast-furnace slag of discharging with Iron and Steel Production, be that the blast furnace water quenching slag is main, mix the byproduct coal ash of discharging therein by the fuel-burning power plant, add gypsum more therein and use more than at least a in sodium sulfate, Tai-Ace S 150, yellow soda ash, aluminic acid soda, the Trisodium Citrate etc. as the ideal additive as the portland cement of alkali-activator and other, these additives play water and or promote setting and harden.

Above-mentioned coal ash contains the very strong solubility sodium oxide of activity degree, and stable, economy is strong, obtains easily, can use coal ash, slag, grog.In addition, if blast furnace water quenching slag basicity more than 1.4, no matter the chemical compositing range in theory could, use may, gypsum no matter be natural, chemical, get rid of gypsum, anhydrous, two water, semi-hydrated gypsum all can use.

The strong early slag coal ash cement of the high-sulfate slag cement of the 1st embodiment of the present invention, high-sulfate slag cement, the blast furnace cement known with the past crowd, coal cement is compared, the advantage that has rapidly sclerosis, epistasis and anti-neutralisation early, the detailed description of its reason, mechanism etc., Shang Weizuo separates bright fully, and considering has following several.

That is to say, the water granulated slag of basicity and chemical composition stability is the prerequisite of intensity property found and stability, non-persistent slag has quick neutralisation when causing immobilization in the low and dry air of wear resistant by the low caused hardness deficiency of intensity to produce the defective of character deterioration.For improving these, blast furnace water quenching slag that uses as main raw material in the invention of first embodiment and coal ash are the glassy phases of control latent hydraulicity and Borazon reaction, and high lime type aluminic acid silicate glass is more than 70% in the water granulated slag.Even, owing to the Al that is solid-solubilized in the above-mentioned glassy phase ₂O ₃, be evenly distributed, the local multi reaction can not take place, so stable.

The soluble alumina of above-mentioned water granulated slag and the total content of silicon are about 49%, and solubility calcium is about 45%, and the soluble alumina of coal ash and the total content of silicon are about 60%.Mixed gypsum and portland cement and in them as a kind of in the sodium sulfate of additive, Tai-Ace S 150, yellow soda ash, aluminic acid soda, Trisodium Citrate etc. or several, and add an amount of water, with its mixing water and, water and initial stage, by the tool slightly acidic that produces by above-mentioned additives decompose such as sodium sulfate, Tai-Ace S 150, yellow soda ash, the aluminium hydroxide Al (OH that adsorptivity is strong ₃), and water and the effect of alkaline NaOH promotes the dissolving of dehydrated gyp-, when adding semi-hydrated gypsum and dihydrate gypsum too, stop calcium-aluminate violent water and, make it normally to condense.

And, grog or gypsum dissolution simultaneously, vitriol and alkali can stimulate the latent hydraulicity of water granulated slag, and the aluminium of water granulated slag, coal ash is worked, and make it to add water decomposition and generate Ca (OH) ₂Generate Al molten in mutually ₂O ₃, SiO ₂, CaO and Calucium Silicate powder water and thing C-S-H and C ₄AH ₁₃, calcium aluminate water and thing, C ₃A or C ₁₂A ₇, C ₃AH ₆, 3 (CA) CaSO ₄Water and separating out of resultant become vigorous, liquid concentration increases, and is hypersaturated state, quick response adds the C of domination early strength ₃A-CaSO ₄-H ₂The high-sulfate type 3CaOAl of O system ₂O ₃3CaSO ₄23H ₂The quick generation of O ettringite is by water and the promoter action promotion 2CaOSiOH of NaOH ₂O, 3CaOSiO ₂H ₂The generation of O Calucium Silicate powder water and thing helps its independent or crisscross water and setting and harden.

As mentioned above, promote a large amount of an ettringite and a sulfate type, 3CaOAl at water and initial stage ₂O ₃CaSO ₄12H ₂The compound generation of O simultaneously constantly generates Calucium Silicate powder water and thing, and the C-S-H gel fills up the gap and the minute aperture of thick ettringite column crystal, begin in early days water and thing and not water and thing be one, form fine and closely woven water and tissue.

For this reason, find early strength, along with water and the gypsum that carries out be consumed, process in time, the ettringite translocation reaction is stable C ₃ACaSO ₄12H ₂O, thereafter, the C-S-H gel continues to generate in the gap of water and thing and capillary interstice, and organize finer and closely wovenization, the water of chronicity by coal ash, water granulated slag, grog and the residue acidic component of being emitted outer 1 and outer 2 developmental stage of mutual diffusion mutually in capillary bore, cause the Borazon reaction of making insoluble compound, C-S-H and C ₄AH ₁₃Precipitation can obtain having filled up the stable hardenite that chemoresistance is arranged capillaceous.Outer 1Al ₂O ₄ ^2-Outer 2SiO ₃ ^2-

Above-mentioned a series of water and reaction are, the chemical constitution that makes the cement main raw material is the high-alumina type, increase the blended amount of gypsum, citric acid as an alkali metal salt of Tai-Ace S 150 or carboxylic acid, the coagulation and water and the effect that are produced when adding water decomposition by other additive, by solute decompose rapidly cause saturated rapidly, promote water and, the setting and harden of time sequence becomes possibility.

In the said process, known in the past high-sulfate slag cement, adding the intensity that causes by the surplus of alkali-activator lowly is, aluminic acid calcium sulfate in the high lime condition of liquid phase is the surface precipitation of the crystallite of water and thing at the unreacted particle, form fine and closely woven resultant layer, be soaking into of anti-sealing, in cut off the water supply and, prevent moving of material, at delay of response, produce intensity find can not phenomenon, in the first embodiment, by the composition that promotes thick ettringite to generate at water and initial stage is carried out upgrading, stop the generation of the crystallite of aluminic acid calcium sulfate water and thing, simultaneously, for obtaining the compound generation of C-S-H water and thing, can obtain the rigid high hardenite of early strength of speed.

In addition because the water of portland cement or grog and, a large amount of Ca (OH) ₂Be in alkaline state between long-term, suppress by CO ₂Soak into the neutralisation that causes of diffusion, prevent the generation of fragile matter part, can obtain the hardenite of stable high-sulfate slag cement.

For strong slag coal ash cement early, compound by above-mentioned water granulated slag and slag makes SiO ₂, Al ₂O ₃, CaO, MgO four-component system be stable, chemical constitution is high-alkali phase, increases the combined amount of gypsum, uses aforementioned additive such as sodium sulfate, it is rigid to make it have speed.

Known blast furnace cement of past and coal ash cement, to formation reaction based on Calucium Silicate powder water and thing, the invention of relevant first embodiment, early strong slag coal ash cement upgrading is formation reaction and the compound generation of water and initial stage ettringite and monosulfate and the chemical constitution of depositing of Calucium Silicate powder water and thing, the combined amount of the gypsum that cooperates is lacked than the high-sulfate slag cement, and is more than blast furnace cement.In addition, above-mentioned morning strong slag coal ash cement the explanation of sclerization be as the criterion with the explanation of aforementioned supersulphated cement.

Because coal ash, gypsum and portland cement or grog constituent are fixed in the specified range according to second embodiment respectively, so obtain than more stabile high-sulfate slag cement of the product of first embodiment and Zao strong slag coal ash cement.

And above-mentioned coal ash preferably uses the standard that meets methylene blue colorimetry and JIS.In addition, the dehydrated gyp-4-18% of aforementioned use, dihydrate gypsum 4-35%, the amount of gypsum that is added will change according to the correlationship of the addition of above-mentioned alkali-activators such as the use level of cement and sodium sulfate.

Manufacture method at the high-sulfate slag cement described in the present invention's the 3rd embodiment, early strong slag coal ash cement, identical with first embodiment, blast furnace water quenching slag 40-80%, and it is identical with the 2nd embodiment, coal ash 3-20%, gypsum 4-35%, portland cement or grog 2-40% add up to 100%, in wherein adding sodium sulfate as additive, Tai-Ace S 150, yellow soda ash, sodium aluminate, Trisodium Citrate one or more then, every kind of 0.5-5%, mix and pulverize or pulverize and mix, because of specific surface area is 4000cm ²/ g-6000cm ²/ g can obtain stabile high grade cement.

In the above-mentioned gypsum, H type dehydrated gyp-is water insoluble, two water, semi-hydrated gypsum water soluble, promote the dissolving of II type dehydrated gyp-by the interpolation of sodium sulfate, can promote dissolving during with use two water, semi-hydrated gypsum equally,, promote the setting and harden of dihydrate gypsum in addition owing to the interpolation of sodium sulfate.

Shown in embodiment of the present invention, in II type dehydrated gyp-, owing to add separately Tai-Ace S 150 or add a kind of in sodium sulfate, yellow soda ash, sodium aluminate, the Trisodium Citrate simultaneously, shown in the aftermentioned embodiment 1-5, can obtain ideal high-sulfate slag cement as additive with it.

In addition, shown in embodiment of the present invention, in dihydrate gypsum,, shown in the aftermentioned embodiment 6-8, can obtain the early strong slag coal ash cement of ideal owing to add sodium sulfate as additive.

Below, 1-8 explains with regard to embodiments of the invention.

Embodiment 1-5 is high-sulfate slag cement and manufacturing process thereof, and embodiment 6-8 is strong slag ash cement of speed and manufacturing process thereof.

Embodiment 1

SiO ₂ 31.00-36.00％

Fe ₂O ₃ 0.03-0.26％

MgO 5.20-5.49％

MnO 0.16-0.48％

Al ₂O ₃ 12.30-14.47％

CaO 28.30-42.42％

SO ₃ 0.88-1.03％

TiO ₂ 0.46-0.82％

Contain above constituent, CaO and SiO ₂Ratio be the blast furnace water quenching slag 66% of 1.6-1.36.

SiO ₂ 34.18-55.06％

Fe ₂O ₃ 4.44-14.84％

MgO 0.19-2.75％

R ₂O 1.66-4.80％

Al ₂O ₃ 17.81-30.59％

CaO 0.66-14.70％

SO ₃ 0.35-10.05％

Contain above constituent, the byproduct coal ash 14% of discharging from the fuel-burning power plant.And this coal ash will meet methylene blue colorimetry and JIS specification.

Change moisture+free water 0.04-0.23%

Al ₂O ₃+Fe ₂O ₃ 2.00-2.30％

MgO 0.11-2.00％

SiO ₂+ insoluble composition 2.00-3.00%

CaO 40.00-42.00％

SO ₃ 50.00-55.50％

Contain above constituent, II type dehydrated gyp-15%.

Loss on ignition 0.33-0.80%

SiO ₂ 20.00-23.00％

Fe ₂O ₃ 2.00-4.00％

MgO 1.00-3.00％

Na ₂O 0.30-0.50％

Insoluble composition 0.01-0.10%

Al ₂O ₃ 4.90-6.00％

CaO 62.00-66.00％

SO ₃ 1.00-2.50％

K ₂O 0.30-0.60％

Contain above constituent, portland cement 5% is a raw material, adds

Tai-Ace S 150 Al ₂(SO ₄) ₃0.5-5% (being preferably 2-4%)

Sodium sulfate Na ₂SO ₄0.5-5% (being preferably 0.5-3%)

Mix, for raising is coagulated hard activity degree with above-mentioned coal ash and other raw material separated pulverizing, all raw materials are pulverized with ball mill with test, and producing the Brian specific surface area is 5500cm ²The high-sulfate slag cement of/g.

The chemical ingredients of the high-sulfate slag cement of embodiment 1 is as follows:

Loss on ignition 0.17%

Insoluble composition 0.10%

SiO ₂ 28.05％

Al ₂O ₃14.21% (solvable composition 12.38%)

Fe ₂O ₃ 1.20％

CaO 40.89％

MgO 3.74％

SO ₃ 10.56％

MnO 0.12％

TiO ₂ 0.37％

R ₂O 0.56％

W/C by 40% adds water than with aforementioned high-sulfate slag cement and mixes, make the mortar that meets JIS R5201, mould notes type toward 4cm * 4cm * 16cm, in room temperature is ± 30 ℃, make test specimen under the condition of humidity more than 80%, in 20 ℃ ± 3 ℃ of temperature, maintenance in the wet box of humidity more than 80%, remove mould after 24 hours, and in 20 ℃ ± 2 ℃ of water temperatures, carried out maintenance in the water.

Test specimen began to condense in 49 minutes, finished by 1 hour 40 minutes.The strength trial result of test specimen is as follows:

Flexural strength (Kg/cm ²)

Material age 3 days 58.45

7 days 70.54

28 days 76.70

Compressive strength (Kg/cm ²)

Material age 3 days 263.38

7 days 385.60

28 days 13.00

Stable test is good

Perform mat, maintenance in the wet steam case 24 hours test specimen put into the water that boils in the container together with sheet glass and heat, crackle and bending are not found in the slowly cooling after 90 minutes of seething with excitement.

Embodiment 2

The same with embodiment 1 employed material, with water granulated slag 63%, coal ash 13%, II type dehydrated gyp-15%, reaching portland cement 10% is raw material, additional sulfuric acid aluminium 0.5-5% (being preferably 2-4%), and yellow soda ash 0.5-5% (being preferably 1-2%) mixes, the same as the test ball mill pulverizing with embodiment 1, making the Brian specific surface area is 4600cm ²The high-sulfate slag cement of/g.

The chemical ingredients of the high-sulfate slag cement of embodiment 2 is as follows:

Loss on ignition 0.20%

Insoluble composition 0.10%

SiO ₂ 29.35％

Al ₂O ₃12.44% (solvable composition 11.66%)

Fe ₂O ₃ 1.31％

CaO 42.47％

MgO 3.89％

SO ₃ 9.10％

MnO 0.13％

TiO ₂ 0.38％

R ₂O 0.59％

The cement of making by embodiment 2 is added water with 42% W/C ratio mixes, make with embodiment 1 measure-alikely, meet the test specimen of JIS R5201, in the damp atmosphere with water in maintenance identical with embodiment 1.

Test specimen began to condense in 41 minutes, finished by 1 hour 38 minutes.The strength trial result of test specimen is as follows:

Flexural strength (Kg/cm ²)

Material age 3 days 54.56

7 days 68.52

28 days 70.30

Compressive strength (kg/cm ²)

Material age 3 days 215.36

7 days 321.60

Stable test in 28 days 430.10 is good

Test conditions is with embodiment 1.

Embodiment 3

The same with embodiment 1 employed material, with water granulated slag 65%, coal ash 10%, II type dehydrated gyp-10%, and portland cement 15% is a raw material, additional sulfuric acid aluminium 0.5-5% (being preferably 2-4%) sodium aluminate 0.5-5% (being preferably 2-3%) mixes, and is the same as the test ball mill pulverizing with embodiment 1, and making the Brian specific surface area is 5000cm ²The high-sulfate slag cement of/g.

The chemical ingredients of the high-sulfate slag cement of embodiment 3 is as follows:

Loss on ignition 0.10%

Insoluble composition 0.10%

SiO ₂ 29.56％

Al ₂O ₃12.09% (solvable composition 11.45%)

Fe ₂O ₃ 1.27％

CaO 44.99％

MgO 3.97％

SO ₃ 6.88％

MnO 0.13％

TiO ₂ 0.39％

R ₂O 0.53％

The cement of making by embodiment 3 is added water with 46% W/C ratio mixes, make with embodiment 1 measure-alikely, meet the test specimen of JIS R5201, in the damp atmosphere with water in maintenance identical with embodiment 1.

Test specimen began to condense in 1 hour 05 minute, finished by 2 hours 05 minute.The strength trial result of test specimen is as follows:

Flexural strength (kg/cm ²)

Material age 3 days 56.25

7 days 68.42

28 days 71.00

Compressive strength (kg/cm ²)

Material age 3 days 220.13

7 days 325.60

28 days 429.10

Stable test is good

Test conditions is with embodiment 1.Embodiment 4

The same with embodiment 1 employed material, with water granulated slag 60%, coal ash 10%, II type dehydrated gyp-10%, and portland cement 20% is a raw material, additional sulfuric acid aluminium 0.5-5% (being preferably 1-2%) mixes, and is the same as the test ball mill pulverizing with embodiment 1, and making the Brian specific surface area is 4550cm ²The high-sulfate slag cement of/g.

The chemical ingredients of the high-sulfate slag cement of embodiment 4 is as follows:

Loss on ignition 0.17%

Insoluble composition 0.03%

SiO ₂ 29.53％

Al ₂O ₃11.67% (solvable composition 11.08%)

Fe ₂O ₃ 1.74％

CaO 46.62％

MgO 4.00％

SO ₃ 5.20％

MnO 0.12％

TiO ₂ 0.35％

R ₂O 0.64％

The cement of making by embodiment 4 is added water with 50% W/C ratio mix, make with embodiment 1 measure-alikely, meet the test specimen of JIS R5201, carried out maintenance in the maintenance and water in the above-mentioned damp atmosphere.

Test specimen began to condense in 1 hour 20 minutes, finished by 2 hours 30 minutes.The strength trial result of test specimen is as follows:

Flexural strength (kg/cm ²)

Material age 3 days 55.32

7 days 64.00

28 days 69.56

Compressive strength (kg/cm ²)

Material age 3 days 235.43

7 days 318.00

28 days 433.15

Stable test is good

Test conditions is with embodiment 1.

Embodiment 5

The same with embodiment 1 employed material, with water granulated slag 58%, coal ash 10%, II type dehydrated gyp-7%, and portland cement 25% is a raw material, additional sulfuric acid aluminium 0.5-5% (being preferably 1-2%) mixes, and is the same as the test ball mill pulverizing with embodiment 1, and making the Brian specific surface area is 4900cm ²The high-sulfate slag cement of/g.

The chemical ingredients of the high-sulfate slag cement of embodiment 5 is as follows:

Loss on ignition 0.17%

Insoluble composition 0.03%

SiO ₂ 29.53％

Al ₂O ₃11.67% (solvable composition 11.08%)

Fe ₂O ₃ 1.74％

CaO 46.62％

MgO 4.00％

SO ₃ 5.29％

MnO 0.12％

TiO ₂ 0.35％

R ₂O 0.64％

The cement of making by embodiment 5 is added water with 50% W/C ratio mixes, make with embodiment 1 measure-alikely, meet the test specimen of JIS R5201, carried out health in health and the water in the fixed damp atmosphere.

Test specimen began to condense in 59 minutes, finished by 1 hour 40 minutes.The strength trial result of test specimen is as follows:

Flexural strength (kg/cm ²)

Material age 3 days 48.93

7 days 64.28

28 days 71.60

Compressive strength (kg/cm ²)

Material age 3 days 225.40

7 days 338.10

28 days 442.30

Stable test is good

Test conditions is with embodiment 1.

Embodiment 6

The same with embodiment 1 employed material, with water granulated slag 60%, coal ash 10%, reaching portland cement 20% and aftermentioned dihydrate gypsum 10% is raw material, additional sulfuric acid sodium 0.5-5% (being preferably 1-2%) mixes, the same as the test ball mill pulverizing with embodiment 1, making the Brian specific surface area is 4800cm ²The morning of/g strong slag coal ash cement.

The constituent of above-mentioned dihydrate gypsum is as follows:

Constitution water 20.92-21.12%

SiO ₂+ insoluble composition 0.20-3.66%

Al ₂O ₃+Fe ₂O ₃ 0.11-2.03％

CaO 23.42-35.35％

MgO 0.20-0.37％

SO ₃ 32.82-46.59％

The morning of embodiment 6, the chemical ingredients of strong slag coal ash cement was as follows:

Loss on ignition 2.15%

Insoluble composition 0.02%

SiO ₂ 29.12％

Al ₂O ₃11.61% (solvable composition 11.07%)

Fe ₂O ₃ 1.43％

CaO 44.83％

MgO 3.73％

SO ₃ 5.80％

MnO 0.12％

TiO ₂ 0.36％

R ₂O 0.59％

The cement of making by embodiment 6 is added water with 50% W/C ratio mixes, make with embodiment 1 measure-alikely, meet the test specimen of JIS R5201, carried out maintenance in maintenance and the water in the fixed damp atmosphere.

Test specimen began to condense in 1 hour 08 minute, finished by 2 hours 00 minute.The strength trial result of test specimen is as follows:

Flexural strength (kg/cm ²)

Material age 3 days 48.75

7 days 65.39

28 days 70.58

Compressive strength (kg/cm ²)

Material age 3 days 224.90

7 days 340.00

28 days 450.23

Stable test is good

Test conditions is with embodiment 1.

Embodiment 7

The same with embodiment 1 employed material, with water granulated slag 60%, coal ash 4%, reaching portland cement 30% and dihydrate gypsum similarly to Example 6 6% is raw material, additional sulfuric acid sodium 0.5-5% (being preferably 1-2%) mixes, the same as the test ball mill pulverizing with embodiment 1, making the Brian specific surface area is 4600cm ²The morning of/g strong slag coal ash cement.

The morning of embodiment 7, the chemical ingredients of strong slag coal ash cement was as follows:

Loss on ignition 1.54%

Insoluble composition 0.03%

SiO ₂ 28.49％

Al ₂O ₃10.46% (solvable composition 10.00%)

Fe ₂O ₃ 1.37％

CaO 49.33％

MgO 3.70％

SO ₃ 3.93％

MnO 0.12％

TiO ₂ 0.36％

R ₂O 0.45％

The cement of making by embodiment 7 is added water with 50% W/C ratio mixes, make with embodiment 1 measure-alikely, meet the test specimen of JIS R5201, carried out maintenance in maintenance and the water in the fixed damp atmosphere.

Test specimen began to condense in 1 hour 08 minute, finished by 2 hours 15 minutes.The strength trial result of test specimen is as follows:

Flexural strength (kg/cm ²)

Material age 3 days 50.07

7 days 63.62

28 days 72.29

Compressive strength (kg/cm ²)

Material age 3 days 225.32

7 days 341.00

28 days 452.18

Stable test is good

Test conditions is with embodiment 1.

Embodiment 8

The same with embodiment 1 employed material, with water granulated slag 50%, coal ash 4%, reaching portland cement 40% and dihydrate gypsum similarly to Example 6 6% is raw material, additional sulfuric acid sodium 0.5-5% (than electing 1-2% as) mixes, the same as the test ball mill pulverizing with embodiment 1, making the Brian specific surface area is 4480cm ²The morning of/g strong slag coal ash cement.

The morning of embodiment 8, the chemical ingredients of strong slag coal ash cement was as follows:

Loss on ignition 1.06%

Insoluble composition 0.04%

SiO ₂ 18.64％

Al ₂O ₃9.68% (solvable composition 9.22%)

Fe ₂O ₃ 1.67％

CaO 60.18％

TiO ₂ 0.30％

R ₂O 0.56％

The cement of making by embodiment 8 is added water with 50% W/C ratio mixes, make with embodiment 1 measure-alikely, meet the test specimen of JIS R5201, carried out maintenance in maintenance and the water in the fixed damp atmosphere.

Test specimen began to condense in 1 hour 10 minutes, finished by 1 hour 50 minutes.The strength trial result of test specimen is as follows:

Flexural strength (kg/cm ²)

Material age 3 days 48.24

7 days 64.35

28 days 70.18

Compressive strength (Kg/cm ²)

Material age 3 days 226.26

7 days 360.33

28 days 461.51

Stable test is good

Test conditions is with embodiment 1.

And the present invention is not limited to the foregoing description, in the scope that does not break away from the specification sheets record, for example makes gypsum with semi-hydrated gypsum, makes additive etc. with Trisodium Citrate, can suitably change.

As mentioned above, the present invention is the blast furnace water quenching Shanghai slag by the byproduct of discharging in the system iron process, the byproduct coal ash that discharge in the fuel-burning power plant, gypsum, portland cement or grog, micropowder after additives such as additional sulfuric acid aluminium add constitutes, and chemical ingredients is a high-alumina, high lime type, the water of aforementioned additive and effect, along with causing that by the micronization of coal ash glassiness specific surface area increases silicon, the solubleness of aluminum oxide just strengthens, and this micropartical enters in the block structure that becomes blocky cement after mixing, the particle that disperses cement, increase can be separated out the space of water and thing, promote cement water and, can obtain following effect.

That is to say that with high-sulfate slag cement known till the present of way, blast furnace cement and coal ash cement are compared, setting rate is fast, early strength and longterm strength height, inhibited oxidation can obtain the early strong slag coal ash cement of the more stable high-sulfate slag cement of chemical.

And aforementioned water granulated slag, coal ash are subjected to any restriction hardly, collect and carry and go up simply easily, add in the manufacturing processed and need not burn till, and as resource-saving, the cement of economizing energy type can be extensive use of, and is cheap.

And the present invention is because to coal ash, gypsum, the constituent of portland cement or grog are limited in the specified range, can obtain more stabile high-quality cement.

The present invention on the water granulated slag identical with claim 2, coal ash, gypsum, portland cement or grog, adds, additives such as Tai-Ace S 150, sodium sulfate, these mix are pulverized+or pulverize and mix, at 4000cm ²/ g-6000cm ²During/g specific surface area, can obtain more stabile high-quality cement.

The present invention is because specific gypsum and additive can obtain the very early strong slag coal ash cement of ideal high-sulfate slag cement.

The symbol corresponding relation of Shi Yonging is as follows in this manual:

R ₂O Na ₂O·K ₂O

C-S-H CaO·SiO ₂·H ₂O

C ₄AH ₁₃ 4CaO·Al ₂O ₃·13H ₂O

C ₃A 3CaO·Al ₂O ₃

C ₁₂A ₇ 12CaO·7Al ₂O ₃

C ₃A·H ₆ 3CaO·Al ₂O ₃·6H ₂O

3(CA)·CaSO ₄ 3(CaO·Al ₂O ₃)·CaSO ₄

Claims

1. the high-sulfate slag cement is characterized in that, said cement is the admixed finepowder end, contains SiO ₂31.00-36.00%, Al ₂O ₃12.30-14.47%, Fe ₂O ₃0.03-0.26%, CaO28.30-42.42%, SO ₃0.88-1.03%, MgO5.20-5.49%, MnO0.16-0.48%, TiO ₂0.46-0.82% is as constituent and CaO/SiO ₂Than byproduct coal ash 3-20%, the gypsum 4-35%, portland cement or the grog 2-40% that discharge for the blast furnace water quenching slag 40-80% of 1.6-1.36, heat power station, add up to 100%, and add at least a in minor amounts of additives sodium sulfate, Tai-Ace S 150, yellow soda ash, sodium aluminate, the Trisodium Citrate therein in addition.

2. cement as claimed in claim 1 is characterized in that containing SiO ₂34.18-55.06%, Al ₂O ₃17.81-30.59%, Fe ₂O ₃4.44-14.83%, CaO0.66-14.7%, MgO0.19-2.75%, SO ₃0.35-10.05%, R ₂O1.66-4.80 is as the coal ash of composition, and gypsum is for containing constitution water+free water 0.04-0.23%, SiO ₂+ insoluble composition 2.00-3.00%, Al ₂O ₃+ Fe ₂O ₃2.00-2.30%, CaO40.00-42.00%, MgO0.11-2.00%, SO ₃50.00-55.50% reaches, contains constitution water 20.92-21.12%, SiO as the II type dehydrated gyp-of composition ₂+ insoluble composition 0.20-3.66%, Al ₂O ₃+ Fe ₂O ₃0.11-2.03%, CaO23.42-35.25%, MgO0.20-0.37%, SO ₃32.82-46.59% is as the dihydrate gypsum of composition,

Portland cement or grog contain, loss on ignition 0.3-0.8%, insoluble composition 0.01-0.10%, SiO ₂20.00-23.00%, Al ₂O ₃4.90-6.00%, Fe ₂O ₃2.00-4.00%, CaO62.00-66.00%, MgO1.00-3.00%, SO ₃1.00-2.50%, Na ₂O0.30-0.50%, K ₂O0.30-0.60% is as composition.

3. the manufacture method of high-sulfate slag cement is characterized in that, contains SiO as composition ₂31.00-36.00%, Al ₂O ₃12.30-14.47%, Fe ₂O ₃0.03-0.26%, CaO28.30-42.42%, MgO5.20-5.49%, SO ₃0.88-1.03%, MnO0.16-0.48%, TiO ₂0.46-0.82%, CaO/SiO ₂For the blast furnace water quenching slag 40-80% of 1.6-1.36 and

Contain SiO ₂34.18-55.06%, Al ₂O ₃17.81-30.59%, Fe ₂O ₃4.44-14.83%, CaO0.06-14.7%, MgO0.19-2.75%, SO ₃0.35-10.05%, R ₂The byproduct coal ash 3-20% that discharges from the fuel-burning power plant of O1.66-4.80% and

Contain constitution water+free water 0.04-0.23%, SiO ₂+ insoluble composition 2.00-3.00%, Al ₂O ₃+ Fe ₂O ₃2.00-2.30%, CaO40.00-42.00%, MgO0.11-2.00%, SO ₃The II type dehydrated gyp-of 50.00-55.50% and contain constitution water 20.92-21.12%, SiO ₂+ insoluble composition 0.20-3.66%, Al ₂O ₃+ Fe ₂O ₃0.11-2.03%, SO ₃One or more gypsum 4-35% of the dihydrate gypsum of 32.82-46.59% and

Contain loss on ignition 0.3-0.8%, insoluble composition 0.01-0.10%, SiO ₂20.00-23.00%, Al ₂O ₃4.90-6.00%, Fe ₂O ₃2.00-4.00%, CaO62.00-66.00%, MgO1.00-3.00%, SO ₃1.00-2.50%, Na ₂0.30-0.50%, K ₂The portland cement of O0.30-0.60% or grog 2-40%, more than each component add up to 100%, in them, add at least a in the sodium sulfate as additive, Tai-Ace S 150, yellow soda ash, sodium aluminate, Trisodium Citrate etc. of 0.5-1.0% again, mix and pulverize or pulverize and mix, specific surface area is 4000cm ²/ g-6000cm ²/ g.

4. the manufacture method of high-sulfate slag cement as claimed in claim 3 is characterized in that containing blast furnace water quenching slag 50-60%.

5. the manufacture method of high-sulfate slag cement as claimed in claim 3 is characterized in that containing coal ash 4-14%.

6. the manufacture method of high-sulfate slag cement as claimed in claim 3 is characterized in that containing portland cement or grog 5-40%.

7. the manufacture method of high-sulfate slag cement as claimed in claim 3, it is characterized in that using II type dehydrated gyp-4-18%, add Tai-Ace S 150 0.5-5% or add a kind of among sodium sulfate 0.5-5%, yellow soda ash 0.5-5%, sodium aluminate 0.5-5%, the Trisodium Citrate 0.5-5% simultaneously with it as additive as gypsum.

8. the manufacture method of high-sulfate slag cement as claimed in claim 7 is characterized in that using II type dehydrated gyp-7-15%.

9. the manufacture method of high-sulfate slag cement as claimed in claim 3 is characterized in that using dihydrate gypsum 4-35% as gypsum, adds sodium sulfate 0.5-5% as additive.

10. the manufacture method of high-sulfate slag cement as claimed in claim 9 is characterized in that using dihydrate gypsum 6-10%.