CN108569855A - A method of improving the air-cooled blast furnace slag hydration activity of low activity - Google Patents
A method of improving the air-cooled blast furnace slag hydration activity of low activity Download PDFInfo
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- CN108569855A CN108569855A CN201810363809.9A CN201810363809A CN108569855A CN 108569855 A CN108569855 A CN 108569855A CN 201810363809 A CN201810363809 A CN 201810363809A CN 108569855 A CN108569855 A CN 108569855A
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- blast furnace
- furnace slag
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- air
- vitreum
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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 of the air-cooled blast furnace slag hydration activity of low activity is improved, building material technical field is belonged to.Blast furnace slag working performance in practical engineering application is poor, so needing to improve its quality during its production process and use, mainly passes through：(1) vitreum network former is added to be modified, the degree of polymerization of the ratio reduction blast furnace slag structure by the way that aluminium oxide, silica adjustment vitreum network former is added, the ratio of aluminium oxide and silica is mainly adjusted by satisfactory flyash.(2) glass volume grid cation modifier is added to be modified, it is modified by the way that barium monoxide, phosphorous oxide is added to reduce the degree of polymerization (3) anion-modified dose of the glass volume grid of addition of blast furnace slag structure, method is that halogen inorganic salts substances are added in slag composition.7day, 28day activity of air-cooled blast furnace slag after improvement can improve 10% or more.
Description
Technical field
A method of the air-cooled blast furnace slag hydration activity of low activity is improved, building material technical field is belonged to.
Background technology
ManUfaCtUre of pig iron will produce many byproducts, and blast furnace slag is one of them.Blast furnace slag with potential hydraulic because live
Property, have become the indispensable functional material of building material field.But by the chemical composition of manUfaCtUre of pig iron raw ore
It influences, chemical composition, mineral composition and its hydraulically active shown of blast furnace slag have differences, different blast furnace slags
28day hydraulically actives can differ tens megapascal or more, and the low hydration activity of part blast furnace slag has seriously affected its working performance,
Building material field is just can be applied to after must being excited to its activity, the main means excited to blast furnace slag have physics
Excitation and chemi-excitation, the fineness that physical excitation relies primarily on raising blast furnace slag increases its specific surface area, to increase its reaction
Area makes hydration activity be improved.Chemi-excitation is then mainly by inorganic salts substance or hydramine substance in aquation mistake
Promote its dissolving in journey to improve its activity.
It is to be determined by the content and its topology convergence degree of its internal active constituent ' vitreum ' on the active nature of blast furnace slag
Fixed, the lower vitreum of the degree of polymerization is more conducive to hydrolyze, and the topology convergence degree of vitreum is related with its chemical composition, institute
With by adjust blast furnace slag chemical composition achieve the purpose that reduce the vitreum degree of polymerization be also improve its hydration activity it is effective
Means, and related art method there is no research to report.There can be a large amount of power consumption using physical excitation for blast furnace slag, drop
Low value-added content of product, and fineness can not accurately control.And then the stimulation effect in practical application can produce for chemi-excitation
Raw unstable phenomenon, same exciting agent can have prodigious difference to the stimulation effect of different blast furnace slags.So from height
It is a kind of effective approach to carry out regulation and control to the hydration activity of blast furnace slag in the structure of clinker, while being swashed with physical excitation and chemistry
It is transported to conjunction, will larger improve the quality of blast furnace slag, is had for application level of the raising blast furnace slag in building materials positive
Facilitation.
Simultaneously in the evolution of air-cooled blast furnace slag granulation device in recent years, the chemically group before blast furnace slag solution slagging
It is this method at one of the main problem for having become designers' consideration with the active theory for adjusting blast furnace slag in structure
In the implementation that modifying agent is added in the forward direction blast furnace slag for carrying out air-cooled granulation provide effective means.
Invention content
The technical problem to be solved in the present invention is to provide a kind of sides that can improve the air-cooled blast furnace slag hydration activity of low activity
Method.
In order to solve the above technical problems, the present invention has pointed out initially that the chemistry of active lower blast furnace slag and structure are special
Sign, 1. such clinker shows lower basicity factor, and 2. such blast furnace slag will present out higher SiO2/Al2O3Than 3. should
There are the indifferent oxides such as a small amount of titanium oxide, manganese oxide in class blast furnace slag.Suitable for a kind of air-cooled blast furnace slag of raising low activity
The blast furnace slag of the method for hydration activity is the lower blast furnace slag of activity caused by the vitreum degree of polymerization is higher, it is characterized in that：
(1) in the chemical composition of the blast furnace slag：Quaternary basicity >=1.2, m (SiO2)/m(Al2O3) >=2.5, Q0/Q1≤ 1,
Wherein Q0For the content of island shape oxygen-octahedron in blast furnace slag vitreum, Q1To contain in blast furnace slag vitreum, there are one bridging oxygens
The content of oxygen-octahedron, the content can pass through29Si MAS NMR quantitative analyses measure.
(2) unfavorable chemical composition present in blast furnace slag is mainly：TiO2、MnO2Etc. inertia or low activity oxide, contain
Amount accounts for 2% or more of blast furnace slag quality.
The main reason for blast furnace slag is applied in cement-based material is that blast furnace slag vitreum issues unboiled water solution in alkaline environment,
Internal Ca2+、Mg2+Equal metal cations enter in aquation slurry, to form gel-like substance, participate in the hardening of cement,
Lower basicity factor can cause effective metal cation in vitreum less, and higher SiO2/Al2O3Glass can then be caused
The increase of internal portion bridging oxygen quantity increases so as to cause the degree of polymerization of vitreum, is unfavorable for hydrolyzing.And by adjusting blast furnace slag
Chemical composition can then improve the problem, and specific method is addition vitreum network former：Silica, aluminium oxide,
Also add vitreum network modifier, including cation modifier BaO and P2O5And anion-modified dose of NaF and NaBr.
The incorporation of barium type oxide a small amount of first can be to introducing Ba inside vitreum2+Cation, barium ions have larger ion half
Diameter can effectively increase the distance between network former in vitreum, to reduce its degree of polymerization, make the silicon in vitreum
Oxygen tetrahedron is from chain (Q1) to island shape change (Q0).And by introducing SiO2/Al2O3It can then be adjusted than the flyash close to 1
Save the SiO of blast furnace slag2/Al2O3Than increasing n (O2-)/[n(Si4+) value, promote to form more island shape silicon inside vitreum
Oxygen tetrahedron (Q0), the bulk polymerization degree of vitreum is reduced, blast furnace slag is made to be more easy to be hydrolyzed under alkaline environment, in addition fine coal
When ash is used as vitreum network former, the quaternary basicity of blast furnace slag entirety can be caused to decline after pickup, but studied
It is smaller to the activity influence of blast furnace slag when 0.5 to show that the variation of quaternary basicity is less than, since the addition of flyash is led in the present invention
The decline of the slag basicity factor of cause is controlled 0.2.And halogen compounds is used as blast furnace slag in hydration process always
Exciting agent, meanwhile, a small amount of halide anion is introduced into the bond energy that can be reduced in vitreum between network former, chemical bond
Energy to failure declines so that the solution rate of system continues to increase, while sodium ion can function as vitreum network modifier, drop
The quantity of bridging oxygen in low vitreum, to reduce the degree of polymerization of vitreum, so in the method, when the addition of halogen compounds
In the forming process of blast furnace slag, rather than in its hydration process.To sum up three kinds of methods, which can act as, improves blast furnace slag
Hydration rate, and improve each active effect of age blast furnace slag.The usage amount of all kinds of chemical substances in the present invention is blast furnace
Slag mass percent：
Vitreum network former：5%-20%.
(a) for basicity factor >=1.2 and m (SiO2)/m(Al2O3The air-cooled blast furnace slag of low activity of) >=2.5, preferred side
Method is that addition vitreum network former is modified.The network former added is satisfactory flyash, volume
It is calculated according to formula 1：
Formula 1：
Wherein M by addition raw material quality, m by the mass percent of oxide, R are corresponded in addition raw material4For original
The basicity factor of beginning blast furnace slag.
(b) for basicity factor >=1.2 and m (SiO2)/m(Al2O3) ＜ 2..5 the air-cooled blast furnace slag of low activity, preferably
Method is to add the one or two of vitreum network modifier.
Glass volume grid cation modifier：0.5%-2%, type are BaO and P2O5One or both of.
Anion-modified dose of glass volume grid：0.5%-2%, type are one or both of NaF and NaBr.
The volume of above-mentioned substance should all be adjusted according to the chemical composition for being enhanced blast furnace slag.
Mass ratio m (the SiO of silica and aluminium oxide in applicable flyash2)/m(Al2O3)≤1.8, Fe2O3Quality point
Number is less than 4%.
Basicity factor is calculated according to formula 2：
Formula 2：
M by the mass percent of oxide is corresponded in addition raw material
Specific implementation mode
Further to illustrate that the present invention is up to the technological means and effect used by expected purpose, with reference to example
The present invention is described in further detail with application case, but they are not limitation of the invention.
It points out initially that, blast furnace slag listed below is dry type air cooling blast furnace slag.
Example 1：
For a kind of blast furnace slag that activity is poor, chemical composition is：
Design technology condition is：Calcination atmosphere is air；Tapping temperature is at 1450 DEG C；Using the air-cooled type of cooling；It rises
Warm system is that dispensing rises to 950 DEG C by room temperature through 20min, keeps the temperature 30min, subsequent temperature of continuing rising, and about 40min, which is burnt to 1450 DEG C, to be melted
State, slag is come out of the stove after keeping the temperature 30min, with fan coolling and is granulated.The activity index of blast furnace slag refers to comparison glue sand and mixes height
Compression strength the ratio between of the two kinds of samples of experiment glue sand of clinker in same age (7d, 28d).According to national standard GB/T 18046-2008
In assay method about activity index, 7 days and 28 days activity indexs are as follows：
Above-mentioned low activity blast furnace slag is adjusted its degree of polymerization using chemical regulation method, by adding fine coal tone
Its whole SiO2/Al2O3The chemical composition of ratio, the flyash of addition is：
The volume for the flyash being calculated according to formula 1 is to add 0.087Kg flyash per 1Kg blast furnace slags.
The chemical composition of blast furnace slag after optimization is：
The design technology condition of blast furnace slag after optimization is：Calcination atmosphere is air；Tapping temperature is at 1450 DEG C；Using wind
The cold type of cooling；Temperature increasing schedule is that dispensing rises to 950 DEG C by room temperature through 20min, keeps the temperature 30min, subsequent temperature of continuing rising, about
40min is burnt to 1450 DEG C of molten conditions, and slag is come out of the stove after keeping the temperature 30min, with fan coolling and is granulated.According to national standard GB/
About the assay method of activity index in T18046-2008,7 days and 28 days activity indexs are as follows：
The SiO of blast furnace slag after optimization2/Al2O31 is reduced compared to former slag, 7day, 28day activity are respectively increased
13% and 11%, its hydration activity is effectively raised, and the main reason for its activity raising is the blast furnace slag vitreum degree of polymerization
It declines to a great extent after optimization.
Example 2：
For a kind of blast furnace slag that activity is poor, chemical composition is：
Design technology condition is：Calcination atmosphere is air；Tapping temperature is at 1450 DEG C；Using the air-cooled type of cooling；It rises
Warm system is that dispensing rises to 950 DEG C by room temperature through 20min, keeps the temperature 30min, subsequent temperature of continuing rising, and about 40min, which is burnt to 1450 DEG C, to be melted
State, slag is come out of the stove after keeping the temperature 30min, with fan coolling and is granulated.The activity index of blast furnace slag refers to comparison glue sand and mixes height
Compression strength the ratio between of the two kinds of samples of experiment glue sand of clinker in same age (7d, 28d).According to national standard GB/T 18046-2008
In assay method about activity index, 7 days and 28 days activity indexs are as follows：
Above-mentioned low activity blast furnace slag is adjusted its degree of polymerization using chemical regulation method, it is micro by adding
BaO adjusts the degree of polymerization of its vitreum.
BaO used is the industrial barium monoxide that purity is 97%, and volume is the 1% of blast furnace slag quality.
The design technology condition of blast furnace slag after optimization is：Calcination atmosphere is air；Tapping temperature is at 1450 DEG C；Using wind
The cold type of cooling；Temperature increasing schedule is that dispensing rises to 950 DEG C by room temperature through 20min, keeps the temperature 30min, subsequent temperature of continuing rising, about
40min is burnt to 1450 DEG C of molten conditions, and slag is come out of the stove after keeping the temperature 30min, with fan coolling and is granulated.The activity index of blast furnace slag
Refer to comparison glue sand and mixes compression strength the ratio between of the two kinds of samples of experiment glue sand in same age (7d, 28d) of blast furnace slag.According to state
It is as follows to mark the assay method about activity index, 7 days and 28 days activity indexs in GB/T 18046-2008：
11% and 12% has been respectively increased in 7day, 28day activity of blast furnace slag after optimization, effectively raises its aquation
Activity, and the main reason for its activity raising is that the blast furnace slag vitreum degree of polymerization declines after optimization.
Example 3：
For a kind of blast furnace slag that activity is poor, chemical composition is：
Design technology condition is：Calcination atmosphere is air；Tapping temperature is at 1450 DEG C；Using the air-cooled type of cooling；It rises
Warm system is that dispensing rises to 950 DEG C by room temperature through 20min, keeps the temperature 30min, subsequent temperature of continuing rising, and about 40min, which is burnt to 1450 DEG C, to be melted
State, slag is come out of the stove after keeping the temperature 30min, with fan coolling and is granulated.The activity index of blast furnace slag refers to comparison glue sand and mixes height
Compression strength the ratio between of the two kinds of samples of experiment glue sand of clinker in same age (7d, 28d).According to national standard GB/T 18046-2008
In assay method about activity index, 7 days and 28 days activity indexs are as follows：
By above-mentioned low activity blast furnace slag, by adding suitable NaBr, adjust its vitreum alkaline environment facile hydrolysis
Performance.
NaBr used is the industrial NaBr that purity is 97%, and volume is the 1% of blast furnace slag quality.
The design technology condition of blast furnace slag after optimization is：Calcination atmosphere is air；Tapping temperature is at 1450 DEG C；Using wind
The cold type of cooling；Temperature increasing schedule is that dispensing rises to 950 DEG C by room temperature through 20min, keeps the temperature 30min, subsequent temperature of continuing rising, about
40min is burnt to 1450 DEG C of molten conditions, and slag is come out of the stove after keeping the temperature 30min, with fan coolling and is granulated.The activity index of blast furnace slag
Refer to comparison glue sand and mixes compression strength the ratio between of the two kinds of samples of experiment glue sand in same age (7d, 28d) of blast furnace slag.According to state
It is as follows to mark the assay method about activity index, 7 days and 28 days activity indexs in GB/T 18046-2008：
8% and 9% has been respectively increased in 7day, 28day activity of blast furnace slag after optimization, effectively raises the work of its aquation
Property.
Claims (4)
1. a kind of method improving the air-cooled blast furnace slag hydration activity of low activity, it is characterised in that：
(a) for basicity factor >=1.2 and m (SiO2)/m(Al2O3The air-cooled blast furnace slag of low activity of) >=2.5 adds vitreum net
Network forming agent is modified；
Its volume is calculated according to formula 1：
Formula 1：
Wherein M by addition raw material quality, m by the mass percent of oxide, R are corresponded in addition raw material4For original blast furnace
The basicity factor of slag；
(b) for basicity factor >=1.2 and m (SiO2)/m(Al2O3) ＜ 2..5 the air-cooled blast furnace slag of low activity, add vitreum
The one or more of network modifier；
The volume of glass volume grid cation modifier is：0.5%-2%, type are BaO and P2O5One or both of；
The volume that anion-modified dose of glass volume grid is：0.5%-2%, type are one or both of NaF and NaBr；
The volume of above-mentioned substance is the mass percent of blast furnace slag.
2. according to the method described in claim 1, it is characterized in that：The mass ratio m of silica and aluminium oxide in flyash
(SiO2)/m(Al2O3)≤1.8, Fe2O3Mass fraction be less than 4%.
3. according to the method described in claim 1, it is characterized in that：The glass volume grid cation modifier is BaO and P2O5
One or both of.
4. according to the method described in claim 1, it is characterized in that：Anion-modified dose of the glass volume grid for NaF and
One or both of NaBr.
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