CN105601117A - Method for one-step forming of microcrystal glass plate through molten-state blast furnace slag - Google Patents
Method for one-step forming of microcrystal glass plate through molten-state blast furnace slag Download PDFInfo
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- CN105601117A CN105601117A CN201610054078.0A CN201610054078A CN105601117A CN 105601117 A CN105601117 A CN 105601117A CN 201610054078 A CN201610054078 A CN 201610054078A CN 105601117 A CN105601117 A CN 105601117A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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Abstract
The invention relates to a method for one-step forming of a microcrystal glass plate through molten-state blast furnace slag. According to the method, the molten-state blast furnace slag and a commercial chemical reagent serve as raw materials, wherein the dosage of the blast furnace slag is 35-70%, and blast furnace slag microcrystal glass is prepared from, by weight, 10-30% of CaO, 35-60% of SiO2, 10-15% of Al2O3, 8-12% of MgO, 2-5% of K2O, 3-4% of ZnO and 3-6% of TiO2; component homogenization of all the materials is completed in a constant-temperature kiln, then the materials are poured into a die, solidification, nucleation, growing and cooling are completed in the die at one step, and finally the microcrystal glass plate is obtained through die release. According to the method, primary sensible heat of the molten-state blast furnace slag is sufficiently and efficiently used, energy waste is avoided, a proper preparing technological process and proper microcrystal glass chemical components are proposed, the preparing steps are simple, cost is low, and a cycle is short.
Description
Technical field
The present invention relates to energy supply for metallurgy reclaims and solid waste high value added utilization technical field, specifically a kind of method of utilizing molten state blast furnace slag one step forming microcrystal glass plate.
Background technology
Utilize the solid waste such as flyash, metallurgical dust mud, cullet, metallurgical slag, more obtained a large amount of research by suitable composition adjustment manufacture devitrified glass. Conventionally, the waste types difference using, the principal crystalline phase of the devitrified glass obtaining is also different, so its physical and chemical performance and mechanical performance also difference is very large.
The main component of blast furnace slag is the oxides such as calcium oxide, silica, aluminium oxide and magnesia, is the good raw material of making devitrified glass. As far back as the sixties in last century, steel research association of Britain just starts to attempt preparing high slag microcrystallite glass, and the former Soviet Union has also almost started similar research work simultaneously. The research in this field recently mainly concentrates on adds nucleating agent to improve crystallization process and the organizational controls of high slag microcrystallite glass. But, the preparation method that these work adopt is the method for traditional melting heat treated, first mixed material is melted, and then coolingly obtains female glass, heated subsequently heat treatment process, heat treatment process often all completes in two steps again. Obviously, such process is not only utilized the heat of high-temperature liquid state blast furnace slag, but also additionally needs a large amount of energy to carry out the melting of material and the heat treatment of female glass.
The sensible heat energy level of blast furnace slag is very high, belongs to high-quality residual heat resources at metallurgy industry. Blast furnace slag is from the temperature of discharging in blast furnace conventionally more than 1450 DEG C, and a contained sensible heat of blast furnace slag per ton is roughly equivalent to the calorific value of 60kg standard coal. Due to the difficulty in recovery technology, the rate of recovery of blast-furnace cement sensible heat is extremely low at present. The most of water quenching that adopts of blast furnace slag of China is produced grain slag, then uses as cement raw material. Although some enterprise utilizes the waste heat of flushing cinder water for heating, can solve the heat supply in plant area's interior section heating or bathroom, but this utilization only accounts for 10% left and right of blast furnace slag complete sensible heat, and be subject to the restriction of time and region, in summer or without the southern area of warming installation, this part energy also can only waste. Meanwhile, granulation of slag technique also needs to waste the water resource of a large amount of preciousnesses. Therefore, if the sensible heat resource of high-temperature molten-state blast furnace slag can be used for to the preparation process of devitrified glass, not only can reclaim the sensible heat of blast furnace slag and reduce cost prepared by devitrified glass, also having significantly improved the value of blast furnace slag simultaneously.
At present, there are some mandates or invention disclosed patent to relate to the utilization of blast furnace slag in microcrystal glass area, as patent of invention [patent No.: 200710054035.3] has proposed a kind of method of utilizing blast furnace slag to prepare devitrified glass, but what use remains cooled solid-state blast furnace slag, then reheat molten state, do not mention the sensible heat that utilizes liquid blast furnace, have the waste of the energy. Patent of invention [application number: 201010274345.8] has proposed to utilize liquid blast furnace directly to make the method for devitrified glass, although utilized the sensible heat of liquid blast furnace, the auxiliary material SiO adding2Must be molten state, and need to shift to an earlier date preheating batching stove to blast furnace tapping temperature, SiO2Melting and batching stove be heated to tapping temperature and need to consume equally a large amount of energy.
The application has the feature of high heating value for molten state blast furnace slag, a kind of method of utilizing molten state blast furnace slag one step forming microcrystal glass plate has been proposed, directly introducing high-temperature liquid state blast furnace slag to composition homogenizes in stove, can greatly save the required outside resources consumption of constant temperature stove, then the high-temperature fusant homogenizing is poured in constant temperature mould, one step complete solidify, forming core and crystallization and finally cooling, shorten the manufacturing cycle, reduce production costs and energy resource consumption.
Summary of the invention
The object of the present invention is to provide a kind of technique simply and efficiently to utilize the method for molten state blast-furnace cement sensible heat one step forming devitrified glass, overcoming existing devitrified glass preparation process complex process, energy resource consumption is large, production cost is high and the deficiency such as the blast-furnace cement sensible heat wasting of resources.
For achieving the above object, the technical solution used in the present invention is:
A method of utilizing molten state blast furnace slag one step forming microcrystal glass plate, comprises the following steps:
(1) consumption of design blast furnace slag is at 35-70%, and the target component of high slag microcrystallite glass (wt.%) is: CaO10-30%, SiO235-60%，Al2O310-15%，MgO8-12%，K2O2-5%，ZnO3-4%，TiO23-6%；
(2) according to the blast furnace slag composition of last heat or front one-time detection and the speed of slagging tap, calculate the various auxiliary material total amounts that need to add and mix auxiliary material according to predetermined devitrified glass composition and add speed, mix auxiliary material and at the uniform velocity join composition homogenize in stove together with high-temperature liquid furnace slag; Composition homogenizes stove constant temperature at 1450-1500 DEG C, and the holdup time that auxiliary material and liquid slag homogenize in stove at composition is more than 1 hour;
(3) composition is homogenized stove discharge the high-temperature molten-state material that completes homogenization of composition be directly poured in thermostatically controlled mould; According to the chemical composition of high slag microcrystallite glass, the constant temperature of mould is between 750-1250 DEG C, and constant temperature time, at 1-3 hour, stops heated at constant temperature subsequently; Molten state high slag microcrystallite glass step in mould completes solidifies, forming core, grows up and naturally cool to room temperature, and the final demoulding obtains the microcrystal glass plate of preset thickness and size.
Blast furnace ironmaking process is the industrial production of a serialization, and the pig iron while at every turn tapping a blast furnace and slag composition all have good continuity with last heat. The present invention, carrying out devitrified glass when batching, is tapped a blast furnace and is slagged tap for the noncontinuity of small blast furnace, with the slag composition of last heat, slag tap time and total quantity of slag represent this original blast furnace slag composition using, slag tap time and the total quantity of slag; Tap a blast furnace and slag tap for the continuity of large blast furnace, can periodically detect slag composition and the calculating speed of slagging tap, the slag composition of front one-time detection and slag tap this original blast furnace slag composition using of speed representation and the speed of slagging tap.
Adopt the present invention of technique scheme, compared with prior art, its advantage is:
The present invention fully and has efficiently utilized a sensible heat of molten state blast furnace slag, has avoided energy waste, has proposed suitable preparation process and devitrified glass chemical composition; The high-temperature molten-state material that completes homogenization of composition of discharging from composition homogenizes stove is directly poured into and can carries out in thermostatically controlled mould, in mould, a step completes and solidifies, forming core, grows up and cooling, without changing stove, the final demoulding obtains the microcrystal glass plate of preset thickness and size, compare mixing and long-time fusion process that conventional art has saved raw material, simplify the preparation process of high slag microcrystallite glass, reduced production cost and manufacturing cycle; The present invention both can meet the production of the extensive devitrified glass of serialization, also can carry out the devitrified glass preparation of small lot or discontinuity; Devitrified glass prepared by the present invention can be used for the ornament materials of building trade, also can be used for the heat-resisting panel of the household articles such as electromagnetic oven.
As preferably, the present invention further technical scheme is:
The consumption of the blast furnace slag in step (1) is 37%, and the devitrified glass principal crystalline phase obtaining is diopside and augite.
In step (2) mix that auxiliary material adds speed=need to add mix auxiliary material total amount/slag tap the time.
In step (2), mix auxiliary material by screw type dispenser feeding to the composition stove that homogenizes.
The homogenize furnace shell of stove of composition in step (2) is tall and thin type, in the middle of burner hearth, be provided with barricade, barricade makes raw material enter from stove one side, flows into stove opposite side from barricade bottom, and flow out from top outlet, last residue is discharged from the sludge discharge tube of stove bottom. Stove is designed to tall and thin type and is provided with barricade in centre, its objective is in order to allow auxiliary material and blast furnace slag carry out sufficient homogenization of composition.
In step (3), the constant temperature of mould is between 1100 DEG C to 1200 DEG C, and constant temperature time is controlled at 1.5 hours.
Mold shell in step (3) is stainless steel, and inside is formed by laying fireproof bricks, and exothermic material is resistance wire or the SiC rod being laid under refractory brick, and temperature is by computer program control.
Brief description of the drawings
Fig. 1 is the process flow diagram of the embodiment of the present invention;
Fig. 2 is SEM (SEM) photo that utilizes a kind of microcrystal glass plate that the present invention makes;
Fig. 3 is X-ray diffraction (XRD) collection of illustrative plates that utilizes the prepared a kind of microcrystal glass plate of the present invention.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further elaborated, but embodiment does not form any restriction to the present invention.
Following embodiment utilizes certain partial melting state slag tapping a blast furnace to carry out at blast furnace discharge yard. Owing to being test-type embodiment, replace the composition stove that homogenizes with the graphite crucible that is placed in resistance furnace at the scene, utilize computer program to set graphite crucible and keep constant temperature, when adding after liquid high temperature furnace slag, the input current of resistance furnace reduces automatically, and molten state blast-furnace cement sensible heat has reduced the required extra power consumption of stove constant temperature. For simulation mixes auxiliary material and liquid blast furnace joins in stove simultaneously, when implementing, embodiment mixes 3 parts of the equal deciles of auxiliary material and liquid slag, mutually intert and add with this, add fast successively in this order graphite crucible: 1/3 liquid slag+1/3 mixes liquid slag+1/3, auxiliary material+1/3 and mixes liquid slag+1/3, auxiliary material+1/3 and mix auxiliary material.
The technological process of following embodiment is referring to Fig. 1.
Embodiment 1:
(1) consumption of design blast furnace slag is 37%, and the target component of high slag microcrystallite glass (wt.%) is: CaO15%, SiO250%，Al2O312%，MgO10%，K2O3%，ZnO3%，TiO25%, other compositions in blast furnace slag are ignored.
(2) the blast furnace slag chemical composition testing result of last heat is CaO40.57%, SiO234.15%，Al2O315.88%，MgO7.88%，K2O0.57%，TiO20.95%, represent the chemical composition of this liquid blast furnace used with this composition detection result. It is 370g that this example is implemented liquid blast furnace used, and as calculated, needed various supplementary product consumptions are respectively: SiO2374g，Al2O361g，MgO71g，K2O27g，TiO246g, ZnO30g by these auxiliary materials and mixing, interts and adds in constant temperature graphite crucible in batches fast together with liquid blast furnace. Graphite crucible was 1460 DEG C of constant temperature 1.5 hours.
(3) complete the liquid blast furnace devitrified glass homogenizing and be poured into constant temperature in the mould of 1120 DEG C, mould pre-set dimension is the grid of 4 12mm × 10mm × 5mm, and constant temperature time is 2 hours. Subsequently, stop mold heated, high slag microcrystallite glass naturally cools to room temperature, and the final demoulding obtains being of a size of 12mm × 10mm × 5mm microcrystal glass plate.
To utilize molten state blast furnace slag one step forming microcrystal glass plate to carry out mensuration and the tissue characterization of X-ray diffraction (XRD), its principal crystalline phase be diopside Ca[MgAl] [SiAl]2O6With augite Ca[Mg0.70Al0.30][Si1.70Al0.30]O6, microcrystal glass plate crystallization is very abundant, as shown in Figures 2 and 3.
Embodiment 2:
(1) consumption of design blast furnace slag is 61.6%, and the target component of high slag microcrystallite glass (wt.%) is: CaO25%, SiO240%，Al2O312%，MgO10%，K2O3%，ZnO3%，TiO25%, other compositions in blast furnace slag are ignored.
(2) the blast furnace slag chemical composition testing result of last heat is CaO40.57%, SiO234.15%，Al2O315.88%，MgO7.88%，K2O0.57%，TiO20.95%, represent the chemical composition of this liquid blast furnace used with this composition detection result. It is 616g that this example is implemented liquid blast furnace used, and as calculated, needed various supplementary product consumptions are respectively: SiO2190g，Al2O322g，MgO52g，K2O26g，TiO244g, ZnO30g by these auxiliary materials and mixing, interts and adds in constant temperature graphite crucible in batches fast together with liquid blast furnace. Graphite crucible was 1460 DEG C of constant temperature 1.5 hours.
(3) complete the liquid blast furnace devitrified glass homogenizing and be poured into constant temperature in the mould of 1200 DEG C, mould pre-set dimension is the grid of 4 12mm × 10mm × 5mm, and constant temperature time is 1.5 hours. Subsequently, stop mold heated, high slag microcrystallite glass naturally cools to room temperature, and the final demoulding obtains being of a size of 12mm × 10mm × 5mm microcrystal glass plate.
To utilize molten state blast furnace slag one step forming microcrystal glass plate to carry out mensuration and the tissue characterization of X-ray diffraction (XRD), its principal crystalline phase be akermanite Ca[Mg0.5Al0.5][Si1.5Al0.5]O7With augite Ca[Mg0.70Al0.30][Si1.70Al0.30]O6, microcrystal glass plate crystallization is very abundant.
Embodiment 3:
(1) consumption of design blast furnace slag is 37%, and the target component of high slag microcrystallite glass (wt.%) is: CaO15%, SiO250%，Al2O312%，MgO10%，K2O3%，ZnO3%，TiO25%, other compositions in blast furnace slag are ignored.
(2) the blast furnace slag chemical composition testing result of last heat is CaO40.57%, SiO234.15%，Al2O315.88%，MgO7.88%，K2O0.57%，TiO20.95%, represent the chemical composition of this liquid blast furnace used with this composition detection result. It is 370g that this example is implemented liquid blast furnace used, and as calculated, needed various supplementary product consumptions are respectively: SiO2374g，Al2O361g，MgO71g，K2O27g，TiO246g, ZnO30g by these auxiliary materials and mixing, interts and adds in constant temperature graphite crucible in batches fast together with liquid blast furnace. Graphite crucible was 1460 DEG C of constant temperature 1.5 hours.
(3) complete the liquid blast furnace devitrified glass homogenizing and be poured into constant temperature in the mould of 1200 DEG C, mould pre-set dimension is the grid of 4 12mm × 10mm × 5mm, and constant temperature time is 1.5 hours. Subsequently, stop mold heated, high slag microcrystallite glass naturally cools to room temperature, and the final demoulding obtains being of a size of 12mm × 10mm × 5mm microcrystal glass plate.
To utilize molten state blast furnace slag one step forming microcrystal glass plate to carry out mensuration and the tissue characterization of X-ray diffraction (XRD), its principal crystalline phase be diopside Ca[MgAl] [SiAl]2O6With augite Ca[Mg0.70Al0.30][Si1.70Al0.30]O6, with respect to example 1 gained microcrystal glass plate, this example gained microcrystal glass plate crystallization is more abundant.
Known by above-mentioned concrete implementation process and interpretation of result, fully and efficiently utilized just a sensible heat of molten state blast furnace slag based on the present invention, add rational composition proportion and optimum preparation condition, not only obtain having that typical thing forms mutually and the high slag microcrystallite glass plate of tissue topography's feature, and reduce energy resource consumption, reduce production cost, shorten manufacturing cycle, can be applicable to well energy supply for metallurgy recovery and devitrified glass and manufacture field, effectively improve comprehensive utilization and the added value thereof of metallurgical industry byproduct.
The foregoing is only the better feasible embodiment of the present invention, not thereby limit to interest field of the present invention, the equivalence that all utilizations description of the present invention and accompanying drawing content are done changes, within being all contained in interest field of the present invention.
Claims (7)
1. a method of utilizing molten state blast furnace slag one step forming microcrystal glass plate, is characterized in that, comprises the following steps:
(1) consumption of design blast furnace slag is at 35-70%, and the target component of high slag microcrystallite glass (wt.%) is: CaO10-30%, SiO235-60%，Al2O310-15%，MgO8-12%，K2O2-5%，ZnO3-4%，TiO23-6%；
(2) according to the blast furnace slag composition of last heat or front one-time detection and the speed of slagging tap, calculate the various auxiliary material total amounts that need to add and mix auxiliary material according to predetermined devitrified glass composition and add speed, mix auxiliary material and at the uniform velocity join composition homogenize in stove together with high-temperature liquid furnace slag; Composition homogenizes stove constant temperature at 1450-1500 DEG C, and the holdup time that auxiliary material and liquid slag homogenize in stove at composition is more than 1 hour;
(3) composition is homogenized stove discharge the high-temperature molten-state material that completes homogenization of composition be directly poured in thermostatically controlled mould; According to the chemical composition of high slag microcrystallite glass, the constant temperature of mould is between 750-1250 DEG C, and constant temperature time, at 1-3 hour, stops heated at constant temperature subsequently; Molten state high slag microcrystallite glass step in mould completes solidifies, forming core, grows up and naturally cool to room temperature, and the final demoulding obtains the microcrystal glass plate of preset thickness and size.
2. the method for utilizing molten state blast furnace slag one step forming microcrystal glass plate according to claim 1, is characterized in that: the consumption of the blast furnace slag in step (1) is 37%, the devitrified glass principal crystalline phase obtaining is diopside and augite.
3. the method for utilizing molten state blast furnace slag one step forming microcrystal glass plate according to claim 1, is characterized in that: in step (2) mix that auxiliary material adds speed=need to add mix auxiliary material total amount/slag tap the time.
4. the method for utilizing molten state blast furnace slag one step forming microcrystal glass plate according to claim 1, is characterized in that: in step (2), mix auxiliary material by screw type dispenser feeding to the composition stove that homogenizes.
5. the method for utilizing molten state blast furnace slag one step forming microcrystal glass plate according to claim 1, it is characterized in that: the homogenize furnace shell of stove of the composition in step (2) is tall and thin type, in the middle of burner hearth, be provided with barricade, barricade makes raw material enter from stove one side, flow into stove opposite side from barricade bottom, and flow out from top outlet, last residue is discharged from the sludge discharge tube of stove bottom.
6. the method for utilizing molten state blast furnace slag one step forming microcrystal glass plate according to claim 1, is characterized in that: in step (3), the constant temperature of mould is between 1100 DEG C to 1200 DEG C, and constant temperature time is controlled at 1.5 hours.
7. utilize according to claim 1 or 5 the method for molten state blast furnace slag one step forming microcrystal glass plate, it is characterized in that: the mold shell in step (3) is stainless steel, inside is formed by laying fireproof bricks, exothermic material is resistance wire or the SiC rod being laid under refractory brick, and temperature is by computer program control.
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Address after: 063210 Tangshan City Caofeidian District, Hebei Province, Tangshan Bay eco Town, Bohai Road, 21 Patentee after: North China Polytechnics Address before: 063009 Xinhua Road 46, Lunan District, Tangshan City, Hebei Patentee before: North China Polytechnics |