CN108569855B - Method for improving hydration activity of low-activity air-cooled blast furnace slag - Google Patents
Method for improving hydration activity of low-activity air-cooled blast furnace slag Download PDFInfo
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- CN108569855B CN108569855B CN201810363809.9A CN201810363809A CN108569855B CN 108569855 B CN108569855 B CN 108569855B CN 201810363809 A CN201810363809 A CN 201810363809A CN 108569855 B CN108569855 B CN 108569855B
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/04—Heat treatment
Abstract
A method for improving the hydration activity of low-activity air-cooled blast furnace slag belongs to the technical field of building materials. The blast furnace slag has poor working performance in practical engineering application, so the quality of the blast furnace slag needs to be improved in the production process and the use process mainly by the following steps: (1) adding a vitreous body network forming agent for modification, adjusting the proportion of the vitreous body network forming agent by adding alumina and silica to reduce the polymerization degree of the blast furnace slag structure, wherein the proportion of the alumina and the silica is mainly adjusted by fly ash meeting the requirements. (2) Adding a vitreous network cation modifier for modification, reducing the polymerization degree of a blast furnace slag structure by adding barium oxide and phosphorus oxide (3), and adding a vitreous network anion modifier for modification. The 7day and 28day activity of the improved air-cooled blast furnace slag can be improved by more than 10 percent.
Description
Technical Field
A method for improving the hydration activity of low-activity air-cooled blast furnace slag belongs to the technical field of building materials.
Background
Smelting pig iron produces many by-products, of which blast furnace slag is one. Blast furnace slag has become an indispensable functional material in the field of building materials because of its latent hydraulic activity. However, under the influence of chemical components of raw ore for smelting pig iron, the chemical composition, mineral composition and hydraulic activity of blast furnace slag are different, the 28day hydraulic activity of different blast furnace slag can be different by more than dozens of megapascals, the low hydration activity of part of blast furnace slag seriously influences the working performance of the blast furnace slag, the blast furnace slag can be applied to the field of building materials after the activity of the blast furnace slag is excited, the main means for exciting the blast furnace slag comprises physical excitation and chemical excitation, and the physical excitation mainly depends on the improvement of the fineness of the blast furnace slag to increase the specific surface area of the blast furnace slag, so that the reaction area of the blast furnace slag is increased, and the hydration activity of the blast furnace slag. The chemical excitation is mainly based on the inorganic salt substance or the alcohol amine substance to promote the dissolution in the hydration process so as to improve the activity.
The activity of the blast furnace slag is essentially determined by the content of an active ingredient 'vitreous body' in the blast furnace slag and the structural polymerization degree of the vitreous body, the lower the polymerization degree is, the more beneficial the vitreous body is to hydrolysis, and the structural polymerization degree of the vitreous body is related to the chemical composition of the vitreous body, so that the purpose of reducing the polymerization degree of the vitreous body by adjusting the chemical composition of the blast furnace slag is also an effective means for improving the hydration activity of the vitreous body, and related technical means are not researched and reported. The blast furnace slag is physically excited, so that a large amount of power consumption exists, the added value of products is reduced, and the fineness cannot be accurately controlled. The excitation effect of chemical excitation in practical application can generate unstable phenomenon, and the excitation effect of the same excitant to different blast furnace slag can have great difference. Therefore, the method is an effective way for regulating and controlling the hydration activity of the blast furnace slag from the structure of the blast furnace slag, and simultaneously, the method is matched with physical excitation and chemical excitation, so that the quality of the blast furnace slag can be greatly improved, and the method has a positive promoting effect on improving the application level of the blast furnace slag in building materials.
Meanwhile, in the development process of the air-cooled blast furnace slag granulation device in recent years, the concept of adjusting the activity of the blast furnace slag from the aspects of chemical composition and structure before the blast furnace slag is dissolved into slag becomes one of the main problems considered by designers, and provides an effective means for adding a modifier into the blast furnace slag before the air-cooled granulation in the method.
Disclosure of Invention
The invention aims to provide a method for improving the hydration activity of low-activity air-cooled blast furnace slag.
In order to solve the technical problems, the invention firstly points out the chemical and structural characteristics of the blast furnace slag with lower activity, firstly, the slag presents lower alkalinity coefficient, and secondly, the blast furnace slag presents higher SiO2/Al2O3And thirdly, a small amount of inert oxides such as titanium oxide, manganese oxide and the like exist in the blast furnace slag. The blast furnace slag suitable for the method for improving the hydration activity of the low-activity air-cooled blast furnace slag is blast furnace slag with low activity caused by high polymerization degree of vitreous bodiesCharacterized in that:
(1) the blast furnace slag comprises the following chemical compositions: quaternary alkalinity is more than or equal to 1.2, m (SiO)2)/m(Al2O3)≥2.5，Q0/Q11 or less, wherein Q0Is the content of isolated silicon-oxygen tetrahedra in the blast furnace slag vitreous body, Q1The blast furnace slag glass body contains a silicon-oxygen tetrahedron with a bridge oxygen content which can be determined by29Si MAS NMR quantitative analysis.
(2) The disadvantageous chemical composition present in blast furnace slag is mainly: TiO 22、MnO2And the content of the inert or low-activity oxides accounts for more than 2 percent of the mass of the blast furnace slag.
The main reason for the application of blast furnace slag in cement-based materials is that blast furnace slag vitreous body is hydrolyzed under alkaline environment, and internal Ca is generated2+、Mg2+When metal cations enter the hydrated slurry, gel substances are formed and participate in the hardening of cement, the lower alkalinity coefficient can lead to less effective metal cations in the glass body, and the higher SiO2/Al2O3This leads to an increase in the amount of internal bridging oxygen in the vitreous body, which leads to an increase in the degree of polymerization of the vitreous body, and is not conducive to hydrolysis. The problem can be improved by adjusting the chemical composition of the blast furnace slag, and the specific method is to add a vitreous network forming agent: silica, alumina, and additional vitreous network modifier including cationic modifier BaO and P2O5And anionic modifiers NaF and NaBr. First, the incorporation of a small amount of barium-based oxide can introduce Ba into the interior of the glass body2+The cation and the barium ion have larger ionic radius, and can effectively increase the distance between the network forming agents in the glass body, thereby reducing the polymerization degree of the network forming agents and leading the silicon-oxygen tetrahedron in the glass body to be in a chain shape (Q)1) Change to island (Q)0). By introducing SiO2/Al2O3The ratio of the fly ash to the fly ash is close to 1, so that the SiO of the blast furnace slag can be adjusted2/Al2O3To increase n (O)2-)/[n(Si4+) The value of (A) promotes formation of more island-like silicon-oxygen tetrahedrons (Q) in the vitreous body0) Lowering the integrity of the vitreous bodyThe polymerization degree enables the blast furnace slag to be hydrolyzed more easily in an alkaline environment, and when the fly ash is added as a vitreous body network forming agent, the whole quaternary alkalinity of the blast furnace slag is reduced after the fly ash is introduced, but researches show that the influence on the activity of the blast furnace slag is small when the quaternary alkalinity is changed to be less than 0.5, and the reduction of the slag alkalinity coefficient caused by the addition of the fly ash is controlled to be 0.2. The halogen compound is always used as an excitant for the blast furnace slag in the hydration process, meanwhile, the introduction of a small amount of halogen anions can reduce the bond energy between network forming agents in the vitreous body, the breaking energy of chemical bonds is reduced, so that the dissolution speed of the system is continuously increased, and simultaneously, sodium ions can also serve as a vitreous body network modifier to reduce the quantity of bridge oxygen in the vitreous body, so that the polymerization degree of the vitreous body is reduced. The three methods can play a role in improving the hydration rate of the blast furnace slag and improving the activity of the blast furnace slag at each age. The using amount of various chemical substances in the invention is that of the blast furnace slag by mass percent:
vitreous network former: 5 to 20 percent.
(a) For alkalinity coefficient more than or equal to 1.2 and m (SiO)2)/m(Al2O3) The low-activity air-cooled blast furnace slag with the activity of being more than or equal to 2.5 is preferably modified by adding a vitreous network forming agent. The added network forming agent is fly ash meeting the requirements, and the mixing amount is calculated according to a formula 1:
equation 1:
wherein M is the mass of the added raw materials, M is the mass percentage of the corresponding oxides in the added raw materials, R4Is the alkalinity coefficient of the original blast furnace slag.
(b) For alkalinity coefficient more than or equal to 1.2 and m (SiO)2)/m(Al2O3) Less than 2, 5, preferably by adding one or both of the glass network modifiersAnd (4) seed preparation.
Vitreous network cationic modifier: 0.5% -2% of BaO and P2O5One or two of them.
Vitreous network anion modifier: 0.5-2% of NaF and one or two of NaBr.
The mixing amount of the substances is adjusted according to the chemical composition of the improved blast furnace slag.
Applicable mass ratio m (SiO) of silicon oxide to aluminum oxide in fly ash2)/m(Al2O3)≤1.8，Fe2O3Is less than 4 percent.
The alkalinity factor is calculated according to equation 2:
equation 2:
m is the mass percentage of the corresponding oxide in the added raw materials
Detailed Description
To further illustrate the technical means and effects of the present invention adopted for the intended purpose, the following detailed description of the present invention is given with reference to the examples and application examples, but they are not intended to limit the present invention.
First, it is noted that the blast furnace slag listed below is dry air-cooled blast furnace slag.
Example 1:
for a less active blast furnace slag, the chemical composition is as follows:
the design process conditions are as follows: the calcining atmosphere is air; the tapping temperature is 1450 ℃; adopting an air cooling mode; the temperature raising system is that the temperature of the ingredients is raised to 950 ℃ from room temperature through 20min, the temperature is kept for 30min, then the temperature is raised continuously, the ingredients are burnt to 1450 ℃ molten state in about 40min, the temperature is kept for 30min, the molten slag is discharged from the furnace, cooled by a fan and granulated. The activity index of the blast furnace slag refers to the ratio of the compressive strength of the comparative mortar and the test mortar mixed with the blast furnace slag in the same age period (7d and 28 d). According to the determination method of the activity index in the national standard GB/T18046-2008, the activity indexes of 7 days and 28 days are as follows:
the polymerization degree of the low-activity blast furnace slag is adjusted by adopting a chemical regulation and control method, and the SiO of the low-activity blast furnace slag is adjusted by adding fly ash2/Al2O3The chemical composition of the added fly ash is as follows:
the blending amount of the fly ash calculated according to the formula 1 is 0.087Kg of fly ash added to every 1Kg of blast furnace slag.
The optimized chemical composition of the blast furnace slag comprises the following components:
the optimized design process conditions of the blast furnace slag are as follows: the calcining atmosphere is air; the tapping temperature is 1450 ℃; adopting an air cooling mode; the temperature raising system is that the temperature of the ingredients is raised to 950 ℃ from room temperature through 20min, the temperature is kept for 30min, then the temperature is raised continuously, the ingredients are burnt to 1450 ℃ molten state in about 40min, the temperature is kept for 30min, the molten slag is discharged from the furnace, cooled by a fan and granulated. According to the determination method of the activity index in the national standard GB/T18046-2008, the activity indexes of 7 days and 28 days are as follows:
optimized SiO of blast furnace slag2/Al2O3Compared with the original slag, the activity of 7day and 28day is respectively improved by 13 percent and 11 percent, and the content of the active ingredients is reduced by 1The hydration activity of the slag is effectively improved, and the main reason for improving the activity is that the polymerization degree of the blast furnace slag vitreous body is greatly reduced after optimization.
Example 2:
for a less active blast furnace slag, the chemical composition is as follows:
the design process conditions are as follows: the calcining atmosphere is air; the tapping temperature is 1450 ℃; adopting an air cooling mode; the temperature raising system is that the temperature of the ingredients is raised to 950 ℃ from room temperature through 20min, the temperature is kept for 30min, then the temperature is raised continuously, the ingredients are burnt to 1450 ℃ molten state in about 40min, the temperature is kept for 30min, the molten slag is discharged from the furnace, cooled by a fan and granulated. The activity index of the blast furnace slag refers to the ratio of the compressive strength of the comparative mortar and the test mortar mixed with the blast furnace slag in the same age period (7d and 28 d). According to the determination method of the activity index in the national standard GB/T18046-2008, the activity indexes of 7 days and 28 days are as follows:
the polymerization degree of the low-activity blast furnace slag is adjusted by adopting a chemical regulation and control method, and the polymerization degree of a vitreous body of the low-activity blast furnace slag is adjusted by adding a trace amount of BaO.
The BaO is industrial barium oxide with the purity of 97 percent, and the mixing amount is 1 percent of the mass of the blast furnace slag.
The optimized design process conditions of the blast furnace slag are as follows: the calcining atmosphere is air; the tapping temperature is 1450 ℃; adopting an air cooling mode; the temperature raising system is that the temperature of the ingredients is raised to 950 ℃ from room temperature through 20min, the temperature is kept for 30min, then the temperature is raised continuously, the ingredients are burnt to 1450 ℃ molten state in about 40min, the temperature is kept for 30min, the molten slag is discharged from the furnace, cooled by a fan and granulated. The activity index of the blast furnace slag refers to the ratio of the compressive strength of the comparative mortar and the test mortar mixed with the blast furnace slag in the same age period (7d and 28 d). According to the determination method of the activity index in the national standard GB/T18046-2008, the activity indexes of 7 days and 28 days are as follows:
the 7day activity and the 28day activity of the optimized blast furnace slag are respectively improved by 11 percent and 12 percent, the hydration activity of the optimized blast furnace slag is effectively improved, and the main reason for improving the activity is that the polymerization degree of the blast furnace slag vitreous body is reduced after the optimization.
Example 3:
for a less active blast furnace slag, the chemical composition is as follows:
the design process conditions are as follows: the calcining atmosphere is air; the tapping temperature is 1450 ℃; adopting an air cooling mode; the temperature raising system is that the temperature of the ingredients is raised to 950 ℃ from room temperature through 20min, the temperature is kept for 30min, then the temperature is raised continuously, the ingredients are burnt to 1450 ℃ molten state in about 40min, the temperature is kept for 30min, the molten slag is discharged from the furnace, cooled by a fan and granulated. The activity index of the blast furnace slag refers to the ratio of the compressive strength of the comparative mortar and the test mortar mixed with the blast furnace slag in the same age period (7d and 28 d). According to the determination method of the activity index in the national standard GB/T18046-2008, the activity indexes of 7 days and 28 days are as follows:
the low-activity blast furnace slag is added with a proper amount of NaBr to adjust the easy hydrolysis performance of the glass body in an alkaline environment.
The NaBr is industrial NaBr with the purity of 97 percent, and the doping amount is 1 percent of the mass of the blast furnace slag.
The optimized design process conditions of the blast furnace slag are as follows: the calcining atmosphere is air; the tapping temperature is 1450 ℃; adopting an air cooling mode; the temperature raising system is that the temperature of the ingredients is raised to 950 ℃ from room temperature through 20min, the temperature is kept for 30min, then the temperature is raised continuously, the ingredients are burnt to 1450 ℃ molten state in about 40min, the temperature is kept for 30min, the molten slag is discharged from the furnace, cooled by a fan and granulated. The activity index of the blast furnace slag refers to the ratio of the compressive strength of the comparative mortar and the test mortar mixed with the blast furnace slag in the same age period (7d and 28 d). According to the determination method of the activity index in the national standard GB/T18046-2008, the activity indexes of 7 days and 28 days are as follows:
the 7day activity and the 28day activity of the optimized blast furnace slag are respectively improved by 8 percent and 9 percent, and the hydration activity of the blast furnace slag is effectively improved.
Claims (1)
1. A method for improving the hydration activity of low-activity air-cooled blast furnace slag is characterized by comprising the following steps:
(a) for quaternary alkalinity coefficient is more than or equal to 1.2 and m (SiO)2)/m(Al2O3) The low-activity air-cooled blast furnace slag with the activity of more than or equal to 2.5 is modified by adding a vitreous body network forming agent;
the mixing amount is calculated according to formula 1:
equation 1:
wherein M is the mass of the added raw materials, M is the mass percentage of the corresponding oxides in the added raw materials, R4The alkalinity coefficient of the original blast furnace slag;
(b) for quaternary alkalinity coefficient is more than or equal to 1.2 and m (SiO)2)/m(Al2O3) Less than 2.5 of low-activity air-cooled blast furnace slag, and one or more than one of vitreous body network modifiers is added;
the mixing amount of the glass network cation modifier is as follows: 0.5% -2% of BaO and P2O5One or two of；
The mixing amount of the glass network anion modifier is as follows: 0.5% -2% of one or two of NaF and NaBr;
the mixing amount of the substances is the mass percentage of the blast furnace slag;
mass ratio m (SiO) of silicon oxide to aluminum oxide in fly ash2)/m(Al2O3)≤1.8，Fe2O3Less than 4% by mass;
the calcining atmosphere is air; the tapping temperature is 1450 ℃; adopting an air cooling mode; the temperature raising system is that the temperature of the ingredients is raised to 950 ℃ from room temperature after 20min, the temperature is kept for 30min, the temperature is raised continuously after 40min, the ingredients are burnt to 1450 ℃ molten state, the temperature is kept for 30min, the molten slag is taken out of the furnace, cooled by a fan and granulated.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008247715A (en) * | 2007-03-30 | 2008-10-16 | Jfe Steel Kk | Sorting method of granulated blast furnace slag for cement, and forming process of cement composition |
| CN101792274A (en) * | 2010-03-19 | 2010-08-04 | 华南理工大学 | Calcium-silicon-aluminum property regulating material for carrying out on-line high-temperature reconstruction on medium-alkalinity steel slag and application thereof |
| CN102249569A (en) * | 2011-07-07 | 2011-11-23 | 王永伯 | Method for improving activity of titanium-containing blast furnace slag |
| CN102382912A (en) * | 2011-11-14 | 2012-03-21 | 中冶南方工程技术有限公司 | Method for treating blast furnace slag |
| CN102815878A (en) * | 2012-08-31 | 2012-12-12 | 中冶南方工程技术有限公司 | Treatment method of gamma-C2S blast furnace slag |
| CN103435278A (en) * | 2013-07-16 | 2013-12-11 | 西安建筑科技大学 | Method for improving hydration activity of steel slag |
| CN103693867A (en) * | 2013-11-25 | 2014-04-02 | 北京工业大学 | High-hydraulic activity blast furnace slag treatment method |
| CN104230198A (en) * | 2014-09-12 | 2014-12-24 | 北京工业大学 | Admixture for increasing activity index of air cooling slag and preparation method thereof |
| CN104844039A (en) * | 2015-04-05 | 2015-08-19 | 北京工业大学 | Additive for improving active index of nickel slag |
-
2018
- 2018-04-22 CN CN201810363809.9A patent/CN108569855B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008247715A (en) * | 2007-03-30 | 2008-10-16 | Jfe Steel Kk | Sorting method of granulated blast furnace slag for cement, and forming process of cement composition |
| CN101792274A (en) * | 2010-03-19 | 2010-08-04 | 华南理工大学 | Calcium-silicon-aluminum property regulating material for carrying out on-line high-temperature reconstruction on medium-alkalinity steel slag and application thereof |
| CN102249569A (en) * | 2011-07-07 | 2011-11-23 | 王永伯 | Method for improving activity of titanium-containing blast furnace slag |
| CN102382912A (en) * | 2011-11-14 | 2012-03-21 | 中冶南方工程技术有限公司 | Method for treating blast furnace slag |
| CN102815878A (en) * | 2012-08-31 | 2012-12-12 | 中冶南方工程技术有限公司 | Treatment method of gamma-C2S blast furnace slag |
| CN103435278A (en) * | 2013-07-16 | 2013-12-11 | 西安建筑科技大学 | Method for improving hydration activity of steel slag |
| CN103693867A (en) * | 2013-11-25 | 2014-04-02 | 北京工业大学 | High-hydraulic activity blast furnace slag treatment method |
| CN104230198A (en) * | 2014-09-12 | 2014-12-24 | 北京工业大学 | Admixture for increasing activity index of air cooling slag and preparation method thereof |
| CN104844039A (en) * | 2015-04-05 | 2015-08-19 | 北京工业大学 | Additive for improving active index of nickel slag |
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