CN102531425A - Composite doping material of air-quenched steel slag and blast furnace slag and preparation method of composite doping material - Google Patents
Composite doping material of air-quenched steel slag and blast furnace slag and preparation method of composite doping material Download PDFInfo
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- CN102531425A CN102531425A CN2011104603771A CN201110460377A CN102531425A CN 102531425 A CN102531425 A CN 102531425A CN 2011104603771 A CN2011104603771 A CN 2011104603771A CN 201110460377 A CN201110460377 A CN 201110460377A CN 102531425 A CN102531425 A CN 102531425A
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Abstract
The invention discloses a composite doping material of air-quenched steel slag and blast furnace slag and a preparation method of the composite doping material. The composite doping material of the air-quenched steel slag and the blast furnace slag comprises less than 20 wt% of the air-quenched steel slag and 50-30 wt% of the blast furnace slag, wherein the air-quenched steel slag comprises the following components of: 40-50 wt% of CaO, 10-20 wt% of SiO2, 0-3 wt% of Al2O3, 5-10 wt% of MgO, 15-25 wt% of TFe and 0-10 wt% of CaO; the grain diameter of the air-quenched steel slag is less than 0.074 mm; the blast furnace slag comprises the following components of: 35-40 wt% of the CaO, 30-40 wt% of the SiO2, 15-20 wt% of the Al2O3, 5-10 wt% of the MgO and 0-3 wt% of S; and the grain diameter of the blast furnace slag is less than 0.074 mm. Therefore, an effective way of utilizing high addition values of the air-quenched steel slag and the blast furnace slag is provided and the cement strength performance is improved to be 1.1-1.5 times as much as the previous cement strength performance; the consumption of cement raw materials is reduced by 30-70 wt% and the carbon dioxide emission in a cement production process is reduced by 30-70 wt%.
Description
Technical field
The present invention relates to building material technical field, more particularly, relate to a kind of gas quench steel slag that is used for cement concrete and blast furnace slag composite blend and preparation method thereof.
Background technology
Slag and blast furnace slag are the by products of steel manufacture process, are mainly derived from steel-making and ironmaking operation.Blast furnace slag 300～400kg that the pig iron per ton produces, slag 80～120kg that steel per ton produces.In output of steel in 2010, the generation of blast furnace slag was about 1.5 hundred million tons then, about 5,600 ten thousand tons of the generation of slag.
The major ingredient of slag and blast furnace slag is CaO, MgO, SiO
2With FeO etc., the free calcium oxide in the slag is meant the quicklime that does not exist with combined form in the grog but exist with unbound state.At present slag mainly adopts fragmentation-screening-magnetic separation treatment process behind the hot application, can reclaim a certain amount of metallic iron, and blast furnace slag mainly adopts the method for shrend, and the main approach that utilizes of slag and blast furnace slag is to make roadbed and backfilling material, and added value is extremely low.Simultaneously, the heat that slag and blast furnace slag contained does not obtain reclaiming.
The a large amount of high basicity converter slag that produces in the process of converter steelmaking is the processing difficult problem that each steelworks is faced always.Slag is made pavement material, backfilling material, building material made requirement slag and is had good stability, and can accomplish a large amount of uses, but added value is lower.Substitute ordinary Portland cement if utilize slag to produce steel furnace slag cement, then not only can produce very big economic benefit, and can reduce the energy consumption of cement products, can play good environmental benefit.Nineteen seventies Research in China success steel furnace slag cement technology, the whole nation has more or less a hundred factory.Country has implemented GB13590-1992 " slag blast-furnace cement " national standard in issue in 1992; Issue YB4098-1996 " slag cement for road ", YB4099-1996 " low-heat slag blast-furnace cement " and YB4099-1996 " slag masonry cement " national sector standard afterwards again, issued and implemented GB/T20491-2006 " steel-making slag powder that is used for cement and concrete " in 2006 again.
Gas quench steel slag is to utilize the method for high pressure nitrogen with the slag granulation, can be rapidly with the slag granulation and reclaim heat.When keeping gas quench steel slag high utilization rate, improve the added value of gas quench steel residue product, become Iron And Steel Industry and carried out the recycling economy urgent problem.
Steel furnace slag cement is as the additive of ordinary Portland cement; Its objective is the slag value-added content of product is increased, therefore improve the prerequisite that the volume of slag in the steel furnace slag cement should guarantee and be: the interpolation of slag can not reduce the performance of ortho-silicate cement.The current steel furnace slag cement that is directed against has been carried out more research; But the big volume steel furnace slag cement that great majority research obtains is not considered above-mentioned prerequisite; The silicate cement or the cement clinker that utilize high grade often obtain more low-grade steel furnace slag cement with addition of the slag and the blast furnace slag of high volume.The steel furnace slag cement that under reduction silicate cement label condition, obtains high volume does not have substantial meaning to improving the slag value-added content of product.
Summary of the invention
The purpose of this invention is to provide a kind of gas quench steel slag and blast furnace slag composite blend and preparation method thereof, improve cement performance and reduce cement raw material consumption.
In order to achieve the above object; The invention provides a kind of gas quench steel slag and blast furnace slag composite blend; Said composite blend comprises the gas quench steel slag that is less than 20wt% and the blast furnace slag of 50-30wt%; Wherein, the composition of gas quench steel slag comprises the CaO of 40-50wt%, the SiO2 of 10-20wt%, the Al of 0-3wt%
2O
3, the MgO of 5-10wt%, the TFe of 15-25wt% and the free CaO of 0-10wt%, the particle diameter of gas quench steel slag is less than 0.074mm, the composition of blast furnace slag comprises the SiO of the CaO of 35-40wt%, 30-40wt%
2, 15-20wt% Al
2O
3, the MgO of 5-10wt% and the S of 0-3wt%, the particle diameter of blast furnace slag is less than 0.074mm.
In order to realize another object of the present invention; A kind of method for preparing gas quench steel slag and blast furnace slag composite blend is provided; Said method comprising the steps of: with slag with the 0.5-2.0 ton/hour speed topple over, carry out wind with the nitrogen of 0.4-0.6Mpa pressure and quench, wind is quenched and is used nitrogen amount 300-350m
3/ h, nitrogen speed is 90-100m/s; Utilize dreg collecting slot to collect slag to slag ladle, with the gas quench steel slag of collection utilize ball mill levigate to particle diameter less than 0.165mm, carry out magnetic separation; Slag after the magnetic separation is continued to be finely ground to particle diameter less than 0.074mm, obtain the gas quench steel slag adulterant in the gas quench steel slag cement adulterant; With the blast furnace utilization ball mill levigate to particle diameter less than 0.074mm, obtain the blast furnace slag adulterant in the gas quench steel slag cement adulterant; The blast furnace slag adulterant of above-mentioned gas quench steel slag adulterant that is less than 20wt% that makes and 50-30wt% is mixed, obtain gas quench steel slag and blast furnace slag composite blend.
In the method for preparing gas quench steel slag and blast furnace slag composite blend according to the embodiment of the invention, slag is to utilize converter to produce the produced simultaneously slag of molten steel, and the composition of slag comprises the SiO of the CaO of 40-50wt%, 10-20wt%
2, 0-3wt% Al
2O
3, the MgO of 5-10wt%, the TFe of 15-25wt% and the free CaO of 0-10wt%; Blast furnace slag is to utilize blast furnace to produce the produced simultaneously blast furnace slag of molten iron, and the composition of blast furnace slag comprises the SiO of the CaO of 35-40wt%, 30-40wt%
2, 15-20wt% Al
2O
3, the MgO of 5-10wt% and the S of 0-3wt%.
In the method for preparing gas quench steel slag and blast furnace slag composite blend according to the embodiment of the invention, said dreg collecting slot is of a size of long 10-30m and wide 1-3m; Said slag ladle is of a size of diameter 0.5-1m and high 1-2m; The power of ball mill is 2-10Kw, and ball material mass ratio is 1 in the ball mill: 1-1: 2.
Compared with prior art, beneficial effect of the present invention is: the first, the high value added utilization for gas quench steel slag and blast furnace slag provides effective way; The second, the strength of cement performance is increased to original 1.1-1.5 doubly; Three, reduce the cement raw material consumption of 30-70wt%; Four, the Carbon emission with cement production process reduces 30-70wt%.
Embodiment
Why slag can be used for producing steel furnace slag cement is because contain tricalcium silicate C in the slag
3S, Dicalcium Phosphate (Feed Grade) β-C
2S, the two content sum accounts for more than 50%, contains C in addition
4AF and C
2F etc. have the mineralogical composition of hydration activity.The hydration process of the hydration activity component in the slag is similar with Portland clinker with hydrated product.The formation temperature that difference is slag than Portland clinker high 200 ℃～300 ℃, cause C in the slag
2S and C
3The S compact crystallization, crystal is thick, and hydration and hardening is slow, but owing to C in the slag
3S phase and β-C
2The S phase content is more much lower than ordinary Portland cement, therefore generally believes that slag is not the fine Portland clinker.But slag can embody the good hydraulicity under the condition that exciting agent exists, the erosion resistance of steel furnace slag cement also is superior to ordinary Portland cement.
In addition, the levigate hydration activity that also can increase slag of steel-making slag powder.The steel-making slag powder granularity diminishes and is actually mechanically excited process.Mechanically excited principle is to improve the fineness of slag with mechanical means, and grinding process is not only the process that particle reduces, the variation of simultaneous material crystalline structure and Surface Physical Chemistry character.Because material specific surface area increases, the part in the grinding energy is converted into ability and surface energy in the newborn particulate.The crystalline bond energy also will change, and lattice energy reduces rapidly, produce lattice dislocation, defective and recrystallization in the position of loss lattice energy.Form amorphous structure soluble in water on the surface.The variation principal reaction of crystalline network is that lattice dimensions reduces, lattice strain increase, structure distort.Lattice dimensions reduces, and guarantees mineral and the long-pending increase of water engaging surface in the slag, and lattice strain increases the reactive force that has improved mineral and water; Structure distorts; Percent crystallinity descends the associative key of mineral crystal is reduced, and water molecules gets into mineral inside easily, quickens hydration reaction.Therefore, mechanical energy can be brought out and produced the chemical reaction that heat energy is difficult to maybe can't bring out generation.
Therefore; The present invention is for solving the high value added utilization problem of gas quench steel slag and blast furnace slag; Proposition is the main material production cement admixture with gas quench steel slag and blast furnace slag, improves cement performance, and the raising strength of cement is 1.1-1.5 a times of Portland cement intensity; And reduce cement raw material consumption 30-70wt%, reduce Carbon emission 30-70wt%.
Below, will describe in detail based on gas quench steel slag of the present invention and blast furnace slag composite blend and preparation method thereof.
Comprise the gas quench steel slag that is less than 20wt% and the blast furnace slag of 50-30wt% according to the gas quench steel slag of the embodiment of the invention and blast furnace slag composite blend, wherein, the composition of gas quench steel slag comprises the CaO of 40-50wt%, the SiO of 10-20wt%
2, 0-3wt% Al
2O
3, the MgO of 5-10wt%, the TFe of 15-25wt% and the free CaO of 0-10wt%, the particle diameter of gas quench steel slag is less than 0.074mm, the composition of blast furnace slag comprises the SiO of the CaO of 35-40wt%, 30-40wt%
2, 15-20wt% Al
2O
3, the MgO of 5-10wt% and the S of 0-3wt%, the particle diameter of blast furnace slag is less than 0.074mm.
In addition, the method for preparing gas quench steel slag and blast furnace slag composite blend according to the present invention may further comprise the steps:
With slag with the 0.5-2.0 ton/hour speed topple over, carry out wind with the nitrogen of 0.4-0.6Mpa pressure and quench, wind is quenched and is used nitrogen amount 300-350m
3/ h, nitrogen speed is 90-100m/s, and wherein, the source of slag is to utilize converter to produce the produced simultaneously slag of molten steel, and the composition of slag comprises the SiO of the CaO of 40-50wt%, 10-20wt%
2, 0-3wt% Al
2O
3, the MgO of 5-10wt%, the TFe of 15-25wt% and the free CaO of 0-10wt%;
Utilize dreg collecting slot to collect slag to slag ladle, dreg collecting slot is of a size of long 10-30m, wide 1-3m, slag ladle diameter 0.5-1m, high 1-2m;
With the gas quench steel slag of collecting utilize ball mill levigate to particle diameter less than 0.165mm, carry out magnetic separation, wherein, ball mill power 2-10Kw, ball material mass ratio is 1: 1-1: 2;
Slag after the magnetic separation is continued to be finely ground to particle diameter less than 0.074mm, obtain the gas quench steel slag adulterant in the gas quench steel slag cement adulterant, stay with subsequent use;
With the blast furnace utilization ball mill levigate to particle diameter less than 0.074mm; Obtain the blast furnace slag adulterant in the gas quench steel slag cement adulterant, stay with subsequent use, wherein; Ball mill power 2-10Kw; Ball material mass ratio is 1: 1-1: 2, and the source of blast furnace slag is to utilize blast furnace to produce the produced simultaneously blast furnace slag of molten iron, the composition of blast furnace slag comprises the SiO of the CaO of 35-40wt%, 30-40wt%
2, 15-20wt% Al
2O
3, the MgO of 5-10wt% and the S of 0-3wt%;
The blast furnace slag adulterant of above-mentioned gas quench steel slag adulterant that is less than 20wt% that makes and 50-30wt% is mixed, obtain gas quench steel slag and blast furnace slag composite blend.
In aforesaid method, should control the particle diameter of the gas quench steel slag of magnetic separation front and back.Specifically, if the particle diameter of gas quench steel slag greater than 0.165mm, then efficiency of magnetic separation reduces, the metallic iron that remains in the slag will reduce the cement intensity of utilizing this composite blend slag preparation; If particle diameter is greater than 0.074mm after the slag fine grinding after the magnetic separation, will influence the intensity of the steel furnace slag cement that utilizes this composite blend slag preparation.
Therefore, gas quench steel slag and blast furnace slag composite blend comprise the gas quench steel slag that is less than 20wt% and the blast furnace slag of 50-30wt% according to an embodiment of the invention, and wherein, the particle diameter of gas quench steel slag is less than 0.074mm, and the particle diameter of blast furnace slag is less than 0.074mm.
Utilization is superior to the performance (regulation of the performance of reference cement is referring to GB/T17671-1999) of reference cement according to the performance (for example, ultimate compression strength, folding strength etc.) of the gas quench steel slag of the method preparation of the embodiment of the invention and the cement that the blast furnace slag composite blend is produced.28 days ultimate compression strength activity indexs according to the cement mortar of GB/T17671-1999 configuration reach more than 1.3, and the ultimate compression strength activity index reached more than 1.1 in 3 days.
Table 1 has provided different gas quench steel slag and the blast furnace slags of composition that is adopted.
Table 1 different tests is with the main chemical compositions (mass percent) of slag
According to the method for preparing gas quench steel slag and blast furnace slag composite blend of the present invention, adulterant that obtains and the cement that makes after reference cement mixes, its performance is superior to reference cement.Through utilizing according to the method for preparing gas quench steel slag and blast furnace slag composite blend of the present invention, first, be that the high value added utilization of gas quench steel slag and blast furnace slag provides effective way; The second, the strength of cement performance is increased to original 1.1-1.5 doubly; Three, reduce the cement raw material consumption of 30-70wt%; Four, the Carbon emission with cement production process reduces 30-70wt%.
Specific embodiment according to the embodiment of the invention will be described below.
Embodiment 1
Gas quench steel slag is finely ground to particle diameter less than 0.165mm, carries out magnetic separation; Slag after the magnetic separation continues to be finely ground to particle diameter less than 0.074mm; Blast furnace slag is finely ground to less than 0.074mm; With the gas quench steel slag of 20wt% and mixed quench steel slag and the blast furnace slag composite blend of bringing about the desired sensation of blast furnace slag of 30wt%, this composite blend is mixed with reference cement, the cement performance that makes is superior to reference cement.28 days ultimate compression strength activity indexs according to the cement mortar of GB/T17671-1999 configuration are that 1.4,3 days ultimate compression strength activity indexs reach more than 1.2.
Embodiment 2
Gas quench steel slag is finely ground to particle diameter less than 0.165mm, carries out magnetic separation; Slag after the magnetic separation continues to be finely ground to particle diameter less than 0.074mm; Blast furnace slag is finely ground to less than 0.074mm; With the gas quench steel slag of 12wt% and blast furnace slag and mixed quench steel slag and the blast furnace slag composite blend of bringing about the desired sensation of reference cement of 46wt%, this composite blend is mixed with reference cement, the cement performance that makes is superior to reference cement.28 days ultimate compression strength activity indexs according to the cement mortar of GB/T17671-1999 configuration are that 1.5,3 days ultimate compression strength activity indexs reach more than 1.25.
Embodiment 3
Gas quench steel slag is finely ground to particle diameter less than 0.165mm, carries out magnetic separation; Slag after the magnetic separation continues to be finely ground to particle diameter less than 0.074mm; Blast furnace slag is finely ground to less than 0.074mm; Gas quench steel slag and the 50wt% blast furnace slag of 0wt% are mixed with reference cement, make gas quench steel slag and blast furnace slag composite blend, this composite blend is mixed with reference cement, the cement performance that makes is superior to reference cement.28 days ultimate compression strength activity indexs according to the cement mortar of GB/T17671-1999 configuration are that 1.66,3 days ultimate compression strength activity indexs reach more than 1.4.
Embodiment 4
Gas quench steel slag is finely ground to particle diameter less than 0.165mm, carries out magnetic separation; Slag after the magnetic separation continues to be finely ground to particle diameter less than 0.074mm; Blast furnace slag is finely ground to less than 0.074mm; Gas quench steel slag and the 38wt% blast furnace slag of 6wt% are mixed with reference cement, make gas quench steel slag and blast furnace slag composite blend, this composite blend is mixed with reference cement, the cement performance that makes is superior to reference cement.28 days ultimate compression strength activity indexs according to the cement mortar of GB/T17671-1999 configuration are that 1.6,3 days ultimate compression strength activity indexs reach more than 1.3.
Compared with prior art, beneficial effect of the present invention is:
1) high value added utilization for gas quench steel slag and blast furnace slag provides effective way;
2) the strength of cement performance is increased to original 1.1-1.5 doubly;
3) the cement raw material consumption of minimizing 30-70wt%;
4) Carbon emission with cement production process reduces 30-70wt%.
It should be noted last that; Above embodiment is only unrestricted in order to the technical scheme of patent of invention; Although with reference to preferred embodiment patent of the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement the technical scheme of patent of the present invention; And not breaking away from the spirit and the scope of patent scheme of the present invention, it all should be encompassed in the middle of the claim scope of patent of the present invention.
Claims (6)
1. gas quench steel slag and blast furnace slag composite blend, wherein, said composite blend comprises the gas quench steel slag that is less than 20wt% and the blast furnace slag of 50-30wt%, wherein, the composition of gas quench steel slag comprises the CaO of 40-50wt%, the SiO of 10-20wt%
2, 0-3wt% Al
2O
3, the MgO of 5-10wt%, the TFe of 15-25wt% and the free CaO of 0-10wt%, the particle diameter of gas quench steel slag is less than 0.074mm, the composition of blast furnace slag comprises the SiO of the CaO of 35-40wt%, 30-40wt%
2, 15-20wt% Al
2O
3, the MgO of 5-10wt% and the S of 0-3wt%, the particle diameter of blast furnace slag is less than 0.074mm.
2. method for preparing gas quench steel slag and blast furnace slag composite blend said method comprising the steps of:
With slag with the 0.5-2.0 ton/hour speed topple over, carry out wind with the nitrogen of 0.4-0.6Mpa pressure and quench, wind is quenched and is used nitrogen amount 300-350m
3/ h, nitrogen speed is 90-100m/s;
Utilize dreg collecting slot to collect slag to slag ladle, with the gas quench steel slag of collection utilize ball mill levigate to particle diameter less than 0.165mm, carry out magnetic separation;
Slag after the magnetic separation is continued to be finely ground to particle diameter less than 0.074mm, obtain the gas quench steel slag adulterant in the gas quench steel slag cement adulterant;
With the blast furnace utilization ball mill levigate to particle diameter less than 0.074mm, obtain the blast furnace slag adulterant in the gas quench steel slag cement adulterant;
The blast furnace slag adulterant of above-mentioned gas quench steel slag adulterant that is less than 20wt% that makes and 50-30wt% is mixed, obtain gas quench steel slag and blast furnace slag composite blend.
3. the method for preparing gas quench steel slag and blast furnace slag composite blend as claimed in claim 2, wherein, slag is to utilize converter to produce the produced simultaneously slag of molten steel, the composition of slag comprises the SiO of the CaO of 40-50wt%, 10-20wt%
2, 0-3wt% Al
2O
3, the MgO of 5-10wt%, the TFe of 15-25wt% and the free CaO of 0-10wt%.
4. the method for preparing gas quench steel slag and blast furnace slag composite blend as claimed in claim 2, wherein, blast furnace slag is to utilize blast furnace to produce the produced simultaneously blast furnace slag of molten iron, the composition of blast furnace slag comprises the SiO of the CaO of 35-40wt%, 30-40wt%
2, 15-20wt% Al
2O
3, the MgO of 5-10wt% and the S of 0-3wt%.
5. the method for preparing gas quench steel slag and blast furnace slag composite blend as claimed in claim 2, wherein, said dreg collecting slot is of a size of long 10-30m and wide 1-3m, and said slag ladle is of a size of diameter 0.5-1m and high 1-2m.
6. the method for preparing gas quench steel slag and blast furnace slag composite blend as claimed in claim 2, wherein, the power of ball mill is 2-10Kw, ball material mass ratio is 1 in the ball mill: 1-1: 2.
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Application publication date: 20120704 |