CN108558246A - A kind of electroslag base mineral admixture and the preparation method and application thereof - Google Patents
A kind of electroslag base mineral admixture and the preparation method and application thereof Download PDFInfo
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- CN108558246A CN108558246A CN201810030589.8A CN201810030589A CN108558246A CN 108558246 A CN108558246 A CN 108558246A CN 201810030589 A CN201810030589 A CN 201810030589A CN 108558246 A CN108558246 A CN 108558246A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/28—Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
- C04B7/425—Acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/47—Cooling ; Waste heat management
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention provides a kind of electroslag base mineral admixtures and preparation method thereof, include the following steps：The mixture of electroslag, slag, cinder and Calcareous material is calcined, electroslag base mineral admixture is obtained.The present invention is modified electroslag by calcining using slag, cinder and Calcareous material as modifying agent, and a large amount of SiO is contained in cinder2And Al2O3, a large amount of SiO is contained in slag2And CaO, and Calcareous material then can directly provide calcium activated, the decomposition such as the mineral such as manganolite, calcium aluminoferrite C 12 A 7 in calcination process in electroslag, slag and cinder without gelation activity, release calcium activated, silicon and aluminium, calcium activated, silicon, aluminium, which reconfigure, at high temperature generates silicate and aluminate with gelation activity, to obtain the excellent electroslag base mineral admixture of gelation activity.
Description
Technical field
The present invention relates to metallurgical slag recycling field more particularly to a kind of electroslag base mineral admixture and its preparation sides
Method and application.
Background technology
Electroslag refers to being diffused using reducing agents such as carbon dust and ferrosilicon powders de- in the reduction period operation of electric-arc furnace steelmaking
Slag is formed by when oxygen.With the development of China's furnace outer refining technology, the quantity of electroslag is also increasing year by year, a large amount of electroslags
Accumulation, not only occupied a large amount of soils, but also cause serious environmental pollution.The essential mineral group of electroslag becomes：Dicalcium silicate
(γ-C2S), C 12 A 7 (C12A7), submellite (C2AS), anorthite (CAS2), manganolite (C3MS2) etc.,
Middle silicate mineral has certain potential gelation activity.But since the silicate mineral phases in electroslag are mainly dicalcium silicate,
And mainly with γ-C2S crystal forms exist, and almost without gelation activity, it is mixed in cement as mineral admixture seriously to limit electroslag
Application in solidifying soil.
Invention content
The purpose of the present invention is to provide a kind of electroslag base mineral admixtures and the preparation method and application thereof.Institute of the present invention
The electroslag base mineral admixture that the preparation method of offer obtains has excellent gelation activity, can be used in cement concrete.
To achieve the above object, the present invention provides a kind of preparation method of electroslag base mineral admixture, including it is as follows
Step：Mixture including electroslag, slag, cinder and Calcareous material is calcined, the blending of electroslag base mineral is obtained
Material.
Preferably, in the mixture, the content of electroslag is 50~60wt.%, the content of slag is 12~
The content of 18wt.%, cinder are 6~8wt.%, and the content of Calcareous material is 20~30wt.%.
Preferably, the slag includes the chemical constituent of following mass content：SiO210~16wt.%, Al2O31~
5wt.%, Fe2O345~55wt.% of 17~23wt.% and CaO.
Preferably, the cinder includes the chemical constituent of following mass content：SiO261~69wt.%, Al2O318~
22wt.%, Fe2O31~3wt.% of 3~7wt.% and CaO.
Preferably, further include auxiliary agent in the mixture；The auxiliary agent is one or both of fluorite and gypsum component
Mixture.
Preferably, the content of auxiliary agent is 0~2wt.% in the mixture, does not include the technical solution that content is 0.
Preferably, the temperature of the calcining is 1200~1500 DEG C, and the time of the calcining is 0.5~2h.
Preferably, further include cooling down after the calcining, the product being cooled to by the calcining in 1~2h is cooled to
150 DEG C or less.
The present invention also provides a kind of electroslag base mineral admixtures, are prepared by above-mentioned technical proposal.
The present invention also provides application of the above-mentioned electroslag base mineral admixture in cementitious material.
The present invention provides a kind of electroslag base mineral admixtures and preparation method thereof, include the following steps：By electroslag,
The mixture of slag, cinder and Calcareous material is calcined, and electroslag base mineral admixture is obtained.The present invention is with slag, coal
Slag and Calcareous material are modifying agent, are modified to electroslag by calcining, and a large amount of SiO is contained in cinder2And Al2O3, steel
Contain a large amount of SiO in slag2And CaO, and Calcareous material then can directly provide calcium activated, electroslag, slag in calcination process
The decomposition such as mineral such as manganolite, calcium aluminoferrite C 12 A 7 with not having gelation activity in cinder, release work
Property calcium, silicon and aluminium, at high temperature calcium activated, silicon, aluminium reconfigure generate with gelation activity silicate and aluminate, to
Obtain the excellent electroslag base mineral admixture of gelation activity.The mineral admixture that preparation method provided by the present invention is obtained
With cement with mass ratio for 3:7 ratio is made into cementitious material, using GB/T 17671-1999 to the gelling property of cementitious material
It is tested, when maintenance 7 days, gelation activity index is up to 110%, and when maintenance 28 days, gelation activity index is up to 99%, explanation
The mineral admixture that preparation method provided by the present invention obtains has excellent gelation activity.
Specific implementation mode
The present invention provides a kind of preparation methods of electroslag base mineral admixture, include the following steps：It will include electric furnace
Slag, slag, cinder and Calcareous material mixture calcined, obtain electroslag base mineral admixture.
In the present invention, in the mixture, the content of electroslag is preferably 50~60wt.%, more preferably 53~
57wt.%.
In the present invention, the preferred ＜ 1wt.% of the water content of the electroslag.In the present invention, when the electroslag raw material
Water content not within the above range when, then the present invention reuses preferably by electroslag raw material drying to required water content.
In the present invention, the drying is preferably forced air drying；The temperature of the drying is preferably 100~200 DEG C, more preferably 130~
160℃；The present invention is not particularly limited the time of the drying, can obtain the electroslag of required water content, at this
In inventive embodiments, the time of the drying is preferably 1~2h, more preferably 1.5~1.8h.
In the present invention, the grain size of the electroslag is preferably≤4.75mm, more preferably≤3mm.
The present invention is not particularly limited the composition of the electroslag, using general electroslag.Of the invention real
It applies in example, the electroslag preferably includes the chemical constituent of following mass content：CaO50~60wt.%, SiO227~
33wt.%, Al2O33~7wt.%, 3~9wt.% of MgO, Fe2O3＜ 1wt.%.The present invention does not have the source of the electroslag
There are particular determination, arbitrary electric furnace steel making gained electroslag.In embodiments of the present invention, the electroslag derives from Baosteel collection
Shaoguan Iron ＆ Steel Plant of group.
In the present invention, the content of slag is preferably 12~18wt.% in the mixture, more preferably 14~
16wt.%.
In the present invention, the slag preferably includes the chemical constituent of following mass content：SiO210~16wt.%,
Al2O31~5wt.%, Fe2O345~55wt.% of 17~23wt.% and CaO；More preferably：SiO211~13wt.%,
Al2O31.5~3wt.%, Fe2O348~50wt.% of 20~22wt.% and CaO.The present invention does not have the source of the slag
Particular determination, in embodiments of the present invention, the slag derive from Shaoguan Iron ＆ Steel Plant of Baoshan Iron and Steel Group.
In the present invention, the grain size of the slag is preferably≤1.18mm, more preferably≤1mm.
In the present invention, the content of cinder is preferably 6~8wt.% in the mixture, more preferably 7~7.5wt.%.
In the present invention, the cinder preferably includes the chemical constituent of following mass content：SiO261~69wt.%,
Al2O318~22wt.%, Fe2O31~3wt.% of 3~7wt.% and CaO；More preferably SiO265~67wt.%, Al2O320
~21wt.%, Fe2O31.5~2wt.% of 4~6wt.% and CaO.The present invention is not particularly limited the source of the cinder,
In embodiments of the present invention, the cinder derives from Shaoguan Iron ＆ Steel Plant of Baoshan Iron and Steel Group.
In the present invention, the grain size of the cinder is preferably≤1.18mm, more preferably≤1mm.
In the present invention, the content of Calcareous material is preferably 20~30wt.% in the mixture, more preferably 25~
27wt.%.In the present invention, the content of the Calcareous material is in terms of CaO.
In the present invention, the Calcareous material is preferably the mixing of one or both of lime stone and white lime component
Object.In the present invention, when the Calcareous material is the mixture of two kinds of components, the proportioning of two kinds of components of the present invention couple is without spy
It is different to limit, arbitrary proportioning may be used.
In the present invention, the grain size of the Calcareous material is preferably≤1.18mm, more preferably≤1mm.
In the present invention, the mixture preferably further includes auxiliary agent.In the present invention, the auxiliary agent is preferably fluorite and stone
The mixture of one or both of cream component.In the present invention, when the auxiliary agent is the mixture of two kinds of components, the present invention couple
The proportioning of two kinds of components is not particularly limited, and arbitrary proportioning may be used.In the present invention, the auxiliary agent is conducive to accelerate mixing
Object melts, and then increases the contact area between each material, promotes chemical reaction.
In the present invention, the grain size of the auxiliary agent is preferably≤1.18mm, more preferably≤1mm.
In the present invention, the content of auxiliary agent is preferably 0~2wt.% in the mixture, does not include the technology that content is 0
Scheme；More preferably 0.6~1wt.%.
The present invention is not particularly limited the order by merging of the mixture, and arbitrary order by merging may be used.
In the present invention, the temperature of the calcining is preferably 1200~1500 DEG C, more preferably 1300~1400 DEG C；It is described
The time of calcining is preferably 0.5~2h, more preferably 1~1.5h.In the present invention, electroslag, slag in the calcination process
The decomposition such as mineral such as manganolite, calcium aluminoferrite C 12 A 7 with not having gelation activity in cinder, release work
Property calcium, silicon and aluminium, at high temperature calcium activated, silicon, aluminium reconfigure generate with gelation activity silicate and aluminate.
After the completion of calcining, product of the present invention preferably by the calcining cools down.In the present invention, the cooling is preferred
To be quickly cooled down.In the present invention, described be quickly cooled down can reduce product crystallization, increase the product of glassy state, further carry
The gelation activity of high product.
In the present invention, the product of the calcining is preferably cooled to 150 DEG C hereinafter, more by the cooling in 1~2h
The product of the calcining is cooled to 80 DEG C preferably in 1~1.5h.In the present invention, the mode of the cooling is preferably wind
It is cold.
After the completion of cooling, the product of the cooling is preferably crushed by the present invention successively, grinding, obtains electroslag Ji Kuang
Polymer blends material.
In the present invention, the Blain specific surface of the electroslag base mineral admixture is preferably 350~450m2/ kg, more
Preferably 400~420m2/kg。
The present invention is not particularly limited broken and grinding the mode and condition, can obtain required Bo Shi and compare table
Area.In embodiments of the present invention, the broken equipment is preferably jaw crusher.In embodiments of the present invention, institute
It is preferably ball milling to state grinding.
The present invention also provides a kind of electroslag base mineral admixtures, are prepared by above-mentioned technical proposal.
The present invention also provides application of the above-mentioned electroslag base mineral admixture in cementitious material.
The present invention is not particularly limited concrete application mode of the electroslag base mineral admixture in cementitious material,
Those skilled in the art can use electroslag base mineral admixture as needed.
In the present invention, the cementitious material preferably includes electroslag base mineral admixture and cement.
In the present invention, content of the electroslag base mineral admixture in cementitious material is preferably 10~50wt.%,
More preferably 30~40wt.%.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
The electroslag, slag, the primary chemical composition of cinder and content are as shown in table 1 below in embodiments of the present invention：
The chemical composition and content of 1 electroslag of table, slag, cinder
Embodiment 1
(1) raw material is uniformly mixed according to following proportioning:Electroslag 54wt.%, slag 15.2wt.%, cinder
7.8wt.%, Calcareous material 23wt.%, obtain mixture；
(2) mixture high temperature furnace is placed in calcine, the temperature of the calcining is 1300 DEG C, the calcining when
Between be 1.5h；
(3) after the completion of calcining, the product progress of the calcining is air-cooled, and the product by the calcining in 1.5h is cooled to
100℃；
(4) use jaw crusher that cooling obtained product is broken for grain size for 4.75mm particles below, using ball
It is 394m that the granular powder is milled to Blain specific surface by grinding machine2/ kg obtains electroslag base mineral admixture.
Match preparing coagulation material by following proportioning：Reference cement 70wt.%, electroslag base mineral admixture 30wt.%, foundation
(GB/T 17671-1999)《Test method for strength of hydraulic cement mortar (ISO methods)》Glue sand performance test is carried out, with the anti-of reference cement
Compressive Strength is standard, calculates the gelation activity index of maintenance 7d and 28d, the results are shown in Table 2.
Embodiment 2
(1) raw material is uniformly mixed according to following proportioning:Electroslag 52wt.%, slag 14.9wt.%, cinder
7.2wt.%, Calcareous material 25.9wt.%, obtain mixture；
(2) mixture high temperature furnace is placed in calcine, the temperature of the calcining is 1300 DEG C, the calcining when
Between be 2h；
(3) after the completion of calcining, the product progress of the calcining is air-cooled, and the product by the calcining in 1.5h is cooled to
100℃；
(4) use jaw crusher that cooling obtained product is broken for grain size for 4.75mm particles below, using ball
It is 408m that the granular powder is milled to Blain specific surface by grinding machine2/ kg obtains electroslag base mineral admixture.
Match preparing coagulation material by following proportioning：Reference cement 70wt.%, electroslag base mineral admixture 30wt.%, foundation
(GB/T 17671-1999)《Test method for strength of hydraulic cement mortar (ISO methods)》Glue sand performance test is carried out, with the anti-of reference cement
Compressive Strength is standard, calculates the gelation activity index of maintenance 7d and 28d, the results are shown in Table 2.
Embodiment 3
(1) raw material is uniformly mixed according to following proportioning:Electroslag 51wt.%, slag 14.7wt.%, cinder
7.4wt.%, Calcareous material 26wt.%, obtain mixture；
(2) mixture high temperature furnace is placed in calcine, the temperature of the calcining is 1300 DEG C, the calcining when
Between be 0.5h；
(3) after the completion of calcining, the product progress of the calcining is air-cooled, and the product by the calcining in 1.5h is cooled to
100℃；
(4) product that jaw crusher cooling will obtain is used to be broken for grain size as the particle of * *, using ball mill by institute
It is 394m to state granular powder and be milled to Blain specific surface2/ kg obtains electroslag base mineral admixture.
Match preparing coagulation material by following proportioning：Reference cement 70wt.%, electroslag base mineral admixture 30wt.%, foundation
(GB/T 17671-1999)《Test method for strength of hydraulic cement mortar (ISO methods)》Glue sand performance test is carried out, with the anti-of reference cement
Compressive Strength is standard, calculates the gelation activity index of maintenance 7d and 28d, the results are shown in Table 2.
Comparative example 1
Match preparing coagulation material by following proportioning：Reference cement 70wt.%, electroslag 30wt.%, according to (GB/T17671-
1999)《Test method for strength of hydraulic cement mortar (ISO methods)》Glue sand performance test is carried out, is mark with the compression strength of reference cement
Standard calculates the gelation activity index of maintenance 7d and 28d, the results are shown in Table 2.
Electroslag base mineral admixture provided by the present invention has excellent gelation activity known to the record of table 2, will
The mineral admixture that preparation method provided by the present invention obtains is with cement with mass ratio for 3:7 ratio is made into cementitious material,
When conserving 7 days, gelation activity index is 95~110%, and when conserving 28 days, gelation activity index is up to 86~99%, i.e., in mine
In the case that the amount of the addition of polymer blends material is larger, the gelation activity of gained cementitious material is still suitable with reference cement, even
It is more excellent；Its gelation activity index is under active the same terms, using the gelation activity for the cementitious material that electroslag is prepared as admixture
1.4 times or more of index, relative to original electroslag, the gelation activity of electroslag base mineral admixture provided by the present invention obtains
To significantly improving.
The gelation activity test result of 2 Examples 1 to 3 of table and comparative example 1
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of electroslag base mineral admixture, includes the following steps：
Mixture including electroslag, slag, cinder and Calcareous material is calcined, the blending of electroslag base mineral is obtained
Material.
2. preparation method as described in claim 1, which is characterized in that in the mixture, the content of electroslag is 50~
60wt.%, the content of slag are 12~18wt.%, and the content of cinder is 6~8wt.%, the content of Calcareous material is 20~
30wt.%.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the slag includes the chemistry of following mass content
Component：SiO210~16wt.%, Al2O31~5wt.%, Fe2O345~55wt.% of 17~23wt.% and CaO.
4. preparation method as claimed in claim 1 or 2, which is characterized in that the cinder includes the chemistry of following mass content
Component：SiO261~69wt.%, Al2O318~22wt.%, Fe2O31~3wt.% of 3~7wt.% and CaO.
5. preparation method as described in claim 1, which is characterized in that further include auxiliary agent in the mixture；The auxiliary agent is
The mixture of one or both of fluorite and gypsum component.
6. preparation method as claimed in claim 5, which is characterized in that the content of auxiliary agent is 0~2wt.% in the mixture,
It does not include the technical solution that content is 0.
7. preparation method as described in claim 1, which is characterized in that the temperature of the calcining is 1200~1500 DEG C, described
The time of calcining is 0.5~2h.
8. preparation method as described in claim 1, which is characterized in that further include cooling after the calcining, it is described to be cooled to 1
The product of the calcining is cooled to 150 DEG C or less in~2h.
9. a kind of electroslag base mineral admixture is prepared by claim 1~8 any one of them preparation method.
10. application of the electroslag base mineral admixture in cementitious material described in claim 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354423A (en) * | 2018-11-07 | 2019-02-19 | 富蕴天山水泥有限责任公司 | A kind of clinker portland cement and preparation method thereof |
| CN114907029A (en) * | 2022-05-31 | 2022-08-16 | 武汉理工大学 | Method for preparing ecological auxiliary cementing material by utilizing high-iron granular slag sintering solid waste |
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