CN104355541A - Black slag micro crystal stone and preparation method thereof - Google Patents
Black slag micro crystal stone and preparation method thereof Download PDFInfo
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- CN104355541A CN104355541A CN201410549844.1A CN201410549844A CN104355541A CN 104355541 A CN104355541 A CN 104355541A CN 201410549844 A CN201410549844 A CN 201410549844A CN 104355541 A CN104355541 A CN 104355541A
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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
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
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Abstract
The invention discloses a black slag micro crystal stone and a preparation method thereof, and relates to the field of manufacturing technologies of glass and building materials. The technical problems of low utilization rate of blast-furnace slag, poor color and poor quality in the prior art that the blast-furnace slag is used as a raw material to be prepared into the slag micro crystal stone are solved. The preparation method is mainly characterized by comprising the following steps: the mixture which is formed by 60-80 parts by weight of blast-furnace slag and 19-47 parts by weight of auxiliary materials is melted to obtain a glass melt, wherein the 19-47 parts by weight of auxiliary materials comprise 10-28 parts by weight of a first modificators for providing silicon dioxide, 5-8 parts by weight of a second modificators for providing sodium elements, 4-9 parts by weight of a nucleating agent and 0-1 part by weight of a reducing agent; the glass melt is shaped into a glass plate material by using a float process technology; the glass plate material is nucleated and crystallized to obtain the black slag micro crystal stone. The prepared black slag micro crystal stone has the advantages of high utilization rate of the blast-furnace slag, pure color, high planeness and high surface quality.
Description
Technical field
The present invention relates to glass, building materials manufacturing process field, particularly relate to a kind of black slag crystallite stone material and preparation method thereof.
Background technology
Crystallite stone material is also called devitrified glass or glass-ceramic, is a kind of novel inorganic non-metallic material of uniqueness.Crystallite stone material just has the performance of many excellences, as high in mechanical strength, chemical stability and Heat stability is good, resistance to wear, corrosion-resistant etc., in fields such as electronics, building, chemical industry, mechanical engineerings as structured material, functional materials, finishing material and obtain widespread use.
A kind of waste residue of discharging from blast furnace when blast furnace slag is manUfaCtUre of pig iron, it belongs to phyllosilicate material, and main component comprises silicon-dioxide, calcium oxide, aluminium sesquioxide, magnesium oxide etc., and blast furnace slag forms molten mass under the high temperature of 1400-1600 DEG C.Along with the development of China's Iron And Steel Industry, blast furnace slag discharge capacity is increasing, and accumulation over the years makes it, and pile up like a mountain, takies a large amount of soils.Because Iron and Steel Enterprises in China adopts water quenching technology process blast furnace warm sludge usually, not only make to dissolve the sensible heat that slag carries and not only do not utilized, also waste valuable water resources, and the sewage that produces of the method and sulfur-bearing steam cause severe contamination to environment.
Main component due to blast furnace slag forms glass especially CaO-Al
2o
3-SiO
2the important component of system glass, and the subsidiary sensible heat of the blast furnace slag energy that to be also later stage glass smelting saving well a large amount of.Therefore, adopt blast furnace slag to be that main raw material prepares high-grade slag crystallite stone material, effectively can reduce the cost of crystallite stone material and solve a difficult problem for the blast furnace slag utilization of resources.
But contriver finds the existence due to calcium contents higher in blast furnace slag and iron, sulphur, carbon, make to be that the vast scale that crystallite stone material prepared by raw material is difficult to realize blast furnace slag adds with blast furnace slag, and the crystallite stone material planeness be prepared into and surface quality poor, and outward appearance is rendered as field gray, shade deviation, be difficult to the accreditation and the popularization that obtain market.
Summary of the invention
In view of this, the embodiment of the present invention provides a kind of black slag crystallite stone material and preparation method thereof, main purpose is realizing the adding rate that in slag crystallite stone material, blast furnace slag is high, and prepare the good black slag crystallite stone material of a kind of pure color, planeness and surface quality.
For achieving the above object, the present invention mainly provides following technical scheme:
On the one hand, embodiments provide a kind of preparation method of black slag crystallite stone material, comprise the steps:
By the mixture that the auxiliary material of the blast furnace slag of 60-80 weight part and 19-47 weight part is formed, carry out founding process and obtain glass melt; Wherein, the auxiliary material of described 19-47 weight part comprises: the reductive agent for providing the second adjusting material of sodium element, the Nucleating Agent of 4-9 weight part and 0-1 weight part for providing the first adjusting material of silicon-dioxide, 4-10 weight part of 10-28 weight part;
Described glass melt float glass process is shaped to glass board material;
Described glass board material is carried out coring, Crystallizing treatment obtains black slag crystallite stone material.
The preparation method of aforesaid black slag crystallite stone material, described first adjusting material selects quartz sand;
Described second adjusting material selects sodium carbonate;
The Nucleating Agent of described 4-10 weight part comprises the Sodium Silicofluoride of the chromite of 2-4 weight part, the titanium dioxide of 0-1 weight part and 2-5 weight part;
Described reductive agent selects coal dust or carbon dust.
The preparation method of aforesaid black slag crystallite stone material, described glass melt comprises following chemical composition: with weight, and silicon-dioxide is 40-53%, and calcium oxide is 20-30%, aluminium sesquioxide is 9-13%, magnesium oxide is 4-5.4%, and ferric oxide is 1.2-2.2%, and chromium sesquioxide is 1.2-2.5%, sodium oxide is 3.4-5.8%, fluorine is 1.2-3.4%, and titanium dioxide is 0-1%, and surplus is inevitable impurity.
The preparation method of aforesaid black slag crystallite stone material, described blast furnace slag is blast furnace water quenching slag;
Wherein, the described mixture formed by the auxiliary material of the blast furnace water quenching slag of 60-80 weight part and 19-47 weight part, carries out founding process and obtains glass melt, be specially:
The blast furnace water quenching slag of 60-80 weight part is mixed with the auxiliary material of 19-47 weight part and obtains mixture;
Described mixture is fed in glass furnace, makes described mixture carry out melting at the temperature of 1450-1500 DEG C, homogenizing, obtain blend melt after clarification.
The preparation method of aforesaid black slag crystallite stone material, described blast furnace slag is the hot melting slag of blast furnace;
Wherein, the mixture of the auxiliary material formation of the hot melting slag of the described blast furnace by 60-80 weight part and 19-47 weight part, carries out founding process and obtains glass melt, be specially:
Hot for the blast furnace of 60-80 weight part melting slag is introduced in glass furnace;
The auxiliary material of the 19-47 weight part mixed is fed in described glass furnace;
Make the hot melting slag of described blast furnace in glass furnace mix formation mixture with described auxiliary material, make described mixture carry out melting at the temperature of 1450-1500 DEG C, homogenizing, obtain blend melt after clarification.
The preparation method of aforesaid black slag crystallite stone material, carries out the step that described glass melt float glass process is shaped to glass board material in molten tin bath;
Wherein, the temperature of described molten tin bath polishing area is 1200-1075 DEG C, and the temperature of described molten tin bath cooling zone is 1050-650 DEG C.
The preparation method of aforesaid black slag crystallite stone material, also comprises before described glass melt float glass process is shaped to the step of glass board material:
When the temperature of described glass melt is reduced to 1250-1300 DEG C, by described glass melt, from being incorporated into described molten tin bath, to carry out float glass process shaping.
The preparation method of aforesaid black slag crystallite stone material, carries out the step obtaining black slag crystallite stone material after described glass board material coring, Crystallizing treatment, is specially in roller kiln:
Described glass board material is warming up to 690-750 DEG C through 30-60min, at 690-750 DEG C, is incubated 60-90min;
Described glass board material is warming up to 860-930 DEG C through 30-60min, at 860-930 DEG C, is incubated 60-90min;
Described glass board material is cooled to less than 80 DEG C through 90-120min, obtains black slag crystallite stone material.
On the other hand, the embodiment of the present invention also provides a kind of black slag crystallite stone material, and described black slag crystallite stone material is made up of the method described in above-mentioned any one.
Aforesaid black slag crystallite stone material, with weight, silicon-dioxide is 40-50%, and calcium oxide is 20-30%, aluminium sesquioxide is 9-12%, magnesium oxide is 4-5.3%, and ferric oxide is 1.2-2.2%, and chromium sesquioxide is 1.2-2.4%, sodium oxide is 3.4-5.8%, fluorine is 1.2-3.4%, and titanium dioxide is 0-1%, and surplus is inevitable impurity.
A kind of black slag crystallite stone material that the embodiment of the present invention proposes and preparation method thereof at least has the following advantages:
(1) the black slag crystallite stone raw material that the present invention proposes is blast furnace slag and auxiliary material, wherein, the adding rate of blast furnace slag is up to more than 60%, the present invention by adopt quartz sand, sodium carbonate, Sodium Silicofluoride, chromite, titanium dioxide and reductive agent as auxiliary material play modified, flux, the effect such as forming core, after shaping, crystallization, annealing, obtain slag crystallite stone material inside by melt and there is unique weave construction, the hypersorption of visible light wave range can be realized, breach the manufacture bottleneck of black slag crystallite stone material.
(2) the present invention is according to material property, the crystallization feature of material composition, floating process is adopted to prepare crystallite stone material, this technique efficiently solves existing preparation technology (casting, calendering formation etc.) due to calcium contents high in glass melt, and cause short, the easy crystallization of material property, make the technical problem that shaping difficulty is large, material road blocks.And the black slag crystallite stone material that the present invention can obtain pure color by this floating preparation process, planeness is high, surface quality is good.
To sum up, black slag crystallite stone material that the present invention proposes and preparation method thereof increases the utilization ratio of blast furnace slag, reduces the raw materials cost of black slag crystallite stone material, and the quality of the black slag crystallite stone material made is better, pure color.
Accompanying drawing explanation
The schema of a kind of black slag microlite material, preparation method that Fig. 1 provides for the embodiment of the present invention.
Embodiment
For further setting forth the present invention for the technique means reaching predetermined goal of the invention and take and effect, below in conjunction with preferred embodiment, to a kind of black slag crystallite stone material proposed according to the present invention and preparation method thereof embodiment, feature and effect thereof, be described in detail as follows.
As shown in Figure 1, the preparation method of the black slag crystallite stone material that the embodiment of the present invention provides mainly comprise the step 1 of carrying out the mixture that blast furnace slag and auxiliary material are formed to found process, the step 2 glass melt float glass process being shaped to glass board material, glass board material carried out coring, Crystallizing treatment step 3 and cut, polish, the step 4 of polishing, specific as follows:
1) by the mixture that the auxiliary material of the blast furnace slag of 60-80 weight part and 19-47 weight part is formed, carry out founding process and obtain glass melt; Wherein, the auxiliary material of described 19-47 weight part comprises: the reductive agent for providing the second adjusting material of sodium ion, the Nucleating Agent of 4-10 weight part and 0-1 weight part for providing the first adjusting material of silicon-dioxide, 5-8 weight part of 10-28 weight part;
Wherein, blast furnace slag is blast furnace water quenching slag or the hot melting slag of blast furnace, in addition, the blast furnace slag chemical composition ranges that the embodiment of the present invention is selected is as follows: with weight, calcium oxide is 35-48%, and silicon-dioxide is 28-42%, and aluminium sesquioxide is 6-18%, magnesium oxide 3-14%, surplus is impurity.
Wherein, if when blast furnace slag selects blast furnace water quenching slag, this step is specially:
Take the blast furnace slag of 60-80 weight part and the auxiliary material of 19-47 weight part, mixed and obtain mixture, mixture is fed in glass furnace and carries out melting, homogenizing, obtain blend melt after clarification.
Wherein, if during the blast furnace slag hot melting slag that is blast furnace, this step is specially:
The blast furnace slag of 60-80 weight part is fed into glass furnace; Be fed in glass furnace after the auxiliary material of 19-47 weight part is mixed; Above-mentioned raw materials stirs and obtains mixture by the stirring system in glass furnace, and this mixture melts in glass furnace, homogenizing, obtain blend melt after clarification.In addition, the hot melting slag of the blast furnace selected is owing to having high sensible heat, and that can improve raw material founds efficiency, and saves the energy prepared glass melt and consume.
Preferably, the temperature of fusion in this step is 1450-1500 DEG C; In this step, blend melt comprises following composition: with weight, silicon-dioxide is 40-53%, calcium oxide is 20-30%, and aluminium sesquioxide is 9-13%, and magnesium oxide is 4-5.4%, ferric oxide is 1.2-2.2%, chromium sesquioxide is 1.2-2.5%, and sodium oxide is 3.4-5.8%, and fluorine is 1.2-3.4%, titanium dioxide is 0-1%, and surplus is inevitable impurity.
Preferably, the first adjusting material selects quartz sand, or other can provide the material of silicon-dioxide (and the addition of material ensures to provide the silicon-dioxide with quartz sand equivalent).Second adjusting material of 5-8 weight part adopts sodium carbonate, and wherein, sodium carbonate not only may be used for providing sodium ion at this, also plays the effect of fluxing, and the speed of melting sources is accelerated; Also sodium sulfate can be adopted to replace sodium carbonate at this.。The Nucleating Agent of 2-5 weight part comprises the Sodium Silicofluoride of the chromite of 2-4 weight part, the titanium dioxide of 0-1 weight part and 2-5 weight part; Sodium Silicofluoride can not only provide sodium element, and fluorine wherein has fluxing and promotes the effect of phase-splitting forming core.Chromite can also ensure that the color and luster of slag crystallite stone material is pure black while promoting forming core crystallization; The granularity of the chromite selected by the embodiment of the present invention is 100-300 order, and wherein the content of chromium sesquioxide is 40-45%, and the content of iron protoxide is 20-15%, remaining as other.Reductive agent selects coal dust or carbon dust.
Other compositions except reductive agent and titanium dioxide in above-mentioned auxiliary material can also use part fluorite (CaF2), albite, iron scale (FeO, Fe2O3) to substitute, and only need ensure that the add-on of auxiliary material can ensure to obtain above-mentioned glass melt chemical composition and content.
Preferably, the proportion optimization of above-mentioned raw materials is: with parts by weight, blast furnace slag 60-65 part, quartz sand 25-28 part, soda ash 6-8 part, Sodium Silicofluoride 2-3 part, chromite 3-4 part, titanium dioxide 0.6-0.8 part, coal dust 0.5-0.8 part.
Preferably, the recrystallization temperature upper limit of the glass melt that this step obtains is higher than 1050 DEG C, and when temperature is 1150 DEG C, the viscosity of this glass melt is lower than 500PaS; When temperature is 950 DEG C, the viscosity 10000PaS of this glass melt.
2) glass melt float glass process is shaped to glass board material;
This step mainly adopts floating process to carry out flat-plate molded to blend melt, is specially: the dog-hole of glass melt in glass furnace, uptake are entered the supply channel in described glass furnace;
When the temperature of glass melt is reduced to 1250-1300 DEG C, by glass melt from supply channel be incorporated into carry out molten tin bath flat-plate molded.
Wherein, the temperature of described molten tin bath polishing area is 1075-1200 DEG C, and the temperature of molten tin bath cooling zone is 1650-1050 DEG C.
In addition, in this step, because glass melt equilibrium thickness is 7-8mm, molten tin bath does not arrange and draws thin shaping district, it is consistent that the speed that glass leaves molten tin bath and glass enter molten tin bath polishing area speed, and glass is at the polishing area residence time 1.5-3min of molten tin bath, according to different drawing thickness (7-15mm), drawing speed range is 72-108 m/h, and molten tin bath is floating throws section length 1.8-5.4m; As 10-15mm heavy sheet glass sheet material need be obtained, barricade need be set in high temperature polishing area to determine thickness and the width of glass strip.
3) black slag crystallite stone material is obtained after glass board material being carried out coring, Crystallizing treatment;
This step is carried out in roller kiln, is specially: the glass board material in roller kiln is warming up to 690-750 DEG C through 30-60min, at 690-750 DEG C, be incubated 60-90min; Be warming up to 860-930 DEG C through 30-60min again, at 860-930 DEG C, be incubated 60-90min; Finally glass board material is cooled to less than 40 DEG C through 90-120min, obtains black slag crystallite stone material.
4) by black slag crystallite stone material cutting good for crystallization, surface finish, polishing, packaging final prod.
Below in conjunction with embodiment, the present invention is described in further detail.
Blast furnace slag used in embodiment one-embodiment four selects the blast furnace waste residue of Ji steel, and it is as follows that it comprises following chemical composition ranges: with weight, and calcium oxide is 36.7%, silicon-dioxide is 36.9%, aluminium sesquioxide is 15.0%, magnesium oxide 6.7%, and surplus is impurity.
In addition, the content of the chromium sesquioxide in chromite used in embodiment one-embodiment four is 44.5%, and the content of iron protoxide is 25.9%, and aluminium sesquioxide is 14.78%, and magnesium oxide is 9.4%, remaining as other.
Embodiment one
1,60 parts of blast furnace water quenching slags, quartz sand 27 parts, soda ash 6 parts, Sodium Silicofluoride 2 parts, chromite 4 parts, titanium dioxide 0.6 part, coal dust 0.4 part are mixed and obtain glass batch.
2, slowly sent in glass furnace by above-mentioned admixtion, controlled melting temperature is 1500 DEG C, after the clarification of the homogenizing of the fusing of 4-6 hour, 2-3 hour and 1-2 hour, obtain available modified glass melt.
Detect the chemical composition of glass melt in this step, make the composition of glass melt be: SiO
2be 52.3%, CaO be 22.9%, Al
2o
3be 9.39%, MgO be 4.16%, Fe
2o
3be 2.15%, Cr
2o
3be 2.5%, Na
2o is 4.23%, F is 1.43%, TiO
2be 0.62%, other: 0.32%.The recrystallization temperature upper limit of glass melt is 1065 DEG C, and during temperature 1150 DEG C, glass melt viscosity is 650PaS, and when temperature is 950 DEG C, glass melt viscosity is 12589PaS.
3, above-mentioned glass melt is entered supply channel through the dog-hole of glass furnace, uptake, when the temperature of glass melt is reduced to 1300 DEG C, through lip tile glass melt is inducted in corresponding molten tin bath and it carried out to float glass process is shaping obtains glass board material.
(condition of molding is: temperature when glass melt enters molten tin bath is 1250 DEG C, and the temperature of molten tin bath polishing area is 1250-1075 DEG C, and cooling zone temperature is 1050-650 DEG C; Molten tin bath arranges graphite barricade and shakeouts thickness to control melt, and obtaining shaped sheet thickness is 12mm, width 1.5m, and the polishing area residence time is 3min, and drawing speed is 72 ms/h, and molten tin bath floating throwing section length is 3.6m, and molten tin bath total length is 22.6m)
4, the glass board material formalized cooling zone is directly sent to through roller-way that roller kiln carry out coring, Crystallizing treatment becomes black slag crystallite stone material.
Concrete coring, Crystallizing treatment parameter are: glass board material is warming up to 750 DEG C through 60min by 650 DEG C and is incubated 1 hour, 860 DEG C of insulation 30min are warming up to again through 30min, be warming up to 930 DEG C through 30min and be incubated 30min, being cooled to 40 DEG C through 120min and going out roller kiln.
5, ask size to cut as required black slag crystallite stone material good for crystallization, and carry out surface finish, polishing, packaging final prod.
Black slag crystallite stone material principal crystalline phase prepared by the present embodiment is particulate Si lime stone and diopside phase, and grain-size is about 100nm, degree of crystallinity about 94%; This black slag crystallite stone material fracture is neat, and exquisite in texture, black is pure.
Embodiment two
1, first 78 parts of molten blast furnace slags are incorporated in glass melter; Then 10 parts of quartz sands, 6 parts of soda ash, 2 parts of Sodium Silicofluorides, 3 parts of chromites, 0.6 part of titanium dioxide and 0.4 part of coal dust are mixed in rear slow feeding glass melter.
2, controlled melting temperature is 1480 DEG C, after fusing in 4-6 hour, 2-3 hour stir homogenizing and clarification in 1-2 hour, obtains available modified glass melt.
Detect the chemical composition of glass melt in this step, make the composition of glass melt be: SiO
2be 41.85%, CaO be 29.9%, Al
2o
3be 12.3%, MgO be 5.4%, Fe
2o
3be 1.9%, Cr
2o
3be 1.9%, Na
2o is 4.3%, F is 1.26%, TiO
2be 0.74%, other are 0.45%.The recrystallization temperature upper limit of this glass melt is 1050 DEG C, and during temperature 1150 DEG C, glass melt viscosity is 500PaS, and when temperature is 950 DEG C, glass melt viscosity is 15849PaS.
3, above-mentioned glass melt is entered supply channel through the dog-hole of glass furnace, uptake, treat that the temperature of glass melt is reduced to 1250 DEG C, glass melt is inducted in corresponding molten tin bath through lip tile and carries out flat-plate moldedly obtaining glass board material to it.
(condition of molding is: temperature when glass melt enters molten tin bath is 1200 DEG C, and the temperature of molten tin bath polishing area is 1075-1200 DEG C, and cooling zone temperature is 1050-650 DEG C; Molten tin bath can not arrange and draw thin shaping district, and glass melt equilibrium thickness is 7.5mm, and arranging strip width is 2m, and the polishing area residence time is 2min, and drawing speed is 108 ms/h, and molten tin bath floating throwing section length is 3.6m, and molten tin bath total length is 25.4m)
4, the glass board material formalized cooling zone is directly sent to through roller-way that roller kiln carry out coring, Crystallizing treatment becomes black slag crystallite stone material.
Concrete coring, Crystallizing treatment parameter are: glass board material is warming up to 690 DEG C through 60min by 650 DEG C and is incubated 1h, then are warming up to 750 DEG C of insulation 30min through 1.5h, be incubated 30min, be cooled to 40 DEG C go out roller kiln through 120min after 60min is warming up to 860 DEG C;
5, ask size to cut as required black slag crystallite stone material good for crystallization, and carry out surface finish, polishing, packaging final prod.
The principal crystalline phase of black slag crystallite stone material prepared by the present embodiment is cluster-shaped gehlenite crystalline phase, degree of crystallinity about 90%; And this black slag crystallite stone material look darkly, fracture is overall, exquisite in texture.
Embodiment three
1,65 parts of blast furnace water quenching slags, quartz sand 26 parts, soda ash 7 parts, Sodium Silicofluoride 2 parts, chromite 3.4 parts-mix are obtained glass batch.
2, slowly sent in glass furnace by above-mentioned admixtion, controlled melting temperature is 1500 DEG C, after the clarification of the homogenizing of the fusing of 4-6 hour, 2-3 hour and 1-2 hour, obtain available modified glass melt.
Detect the chemical composition of glass melt in this step, make the composition of glass melt be: SiO
2be 50.8%, CaO be 24.8%, Al
2o
3be 9.8%, MgO be 4.86%, Fe
2o
3be 1.87%, Cr
2o
3be 2.2%, Na
2o to be 4.23%, F be 1.30% other: 0.14%.The recrystallization temperature upper limit of glass melt is 1060 DEG C, and during temperature 1150 DEG C, glass melt viscosity is 640PaS, and when temperature is 950 DEG C, glass melt viscosity is 12889PaS.
3, above-mentioned glass melt is entered supply channel through the dog-hole of glass furnace, uptake, when the temperature of glass melt is reduced to 1300 DEG C, glass melt is inducted in corresponding molten tin bath through lip tile and carries out flat-plate moldedly obtaining glass board material to it.
(condition of molding is: temperature when glass melt enters molten tin bath is 1250 DEG C, and the temperature of molten tin bath polishing area is 1075-1250 DEG C, and cooling zone temperature is 1050-650 DEG C; Molten tin bath is provided with graphite barricade and shakeouts thickness to control melt, and obtaining shaped sheet thickness is 15mm, width 1.2m, and the polishing area residence time is 3min, and drawing speed is 72 ms/h, and molten tin bath floating throwing section length is 3.6m, and molten tin bath total length is 22.6m)
4, the glass board material formalized cooling zone is directly sent to through roller-way that roller kiln carry out coring, Crystallizing treatment becomes black slag crystallite stone material.
Concrete coring, Crystallizing treatment parameter are: glass board material is warming up to 750 DEG C through 60min by 650 DEG C and is incubated 1 hour, 860 DEG C of insulation 30min are warming up to again through 30min, be warming up to 900 DEG C through 30min and be incubated 30min, being cooled to 40 DEG C through 120min and going out roller kiln.
5, black slag crystallite stone plate good for crystallization is cut by demand size, and carry out surface finish, polishing, packaging final prod.
The principal crystalline phase of black slag crystallite stone material prepared by the present embodiment is chain, corynebacterium shape gehlenite crystalline phase, and grain-size is about 500nm-1um, degree of crystallinity about 80%.The black slag crystallite stone material that in addition prepared by the present embodiment is overall rough break, and outward appearance is light black.
Embodiment four
1,70 parts of hot melting slags of blast furnace are incorporated in glass melter; Then quartz sand 18 parts, soda ash 7 parts, Sodium Silicofluoride 5 parts, chromite 3 parts, titanium dioxide 0.7 part, coal dust 0.5 part are mixed in rear slow feeding glass melter.
2, controlled melting temperature is 1500 DEG C, after the clarification of the homogenizing of the fusing of 4-6 hour, 2-3 hour and 1-2 hour, obtain available modified glass melt.
Detect the chemical composition of glass melt in this step, make the composition of glass melt be: SiO
2for 44.849.2%, CaO are 26.4%, Al
2o
3be 10.5%, MgO be 4.66%, Fe
2o
3be 1.98%, Cr
2o
3for-1.98%, Na
2o is 6.23%, F is 2.30%, TiO
2be 0.65%, other: 0.48%.The recrystallization temperature upper limit of this glass melt is 1055 DEG C, and during temperature 1150 DEG C, glass melt viscosity is 560PaS, and when temperature is 950 DEG C, glass melt viscosity is 14849PaS.
3, above-mentioned glass melt is entered supply channel through the dog-hole of glass furnace, uptake, when the temperature of glass melt is reduced to 1250 DEG C, glass melt is inducted in corresponding molten tin bath through lip tile and carries out flat-plate moldedly obtaining glass board material to it.
(condition of molding is: temperature when glass melt enters molten tin bath is 1250 DEG C, and the temperature of molten tin bath polishing area is 1075-1250 DEG C, and cooling zone temperature is 1050-650 DEG C; Molten tin bath does not arrange and draws thin shaping district, and glass melt equilibrium thickness is 7.5mm, and arranging strip width is 2m, and the polishing area residence time is 2.5min, and drawing speed is 90 ms/h, and molten tin bath floating throwing section length is 3.8m, and molten tin bath total length is 27m)
4, the glass board material formalized cooling zone is directly sent to through roller-way that roller kiln carry out coring, Crystallizing treatment becomes black slag crystallite stone material.
Concrete coring, Crystallizing treatment parameter are: glass board material is warming up to 750 DEG C through 60min by 650 DEG C and is incubated 1.5 hours, then are warming up to 860 DEG C of insulation 60min through 30min, be cooled to 40 DEG C go out roller kiln through 120min.
5, black slag crystallite stone plate good for crystallization is cut by demand size, and carry out surface finish, polishing, packaging final prod.
The principal crystalline phase of black slag crystallite stone material prepared by the present embodiment is particulate state diopside phase, degree of crystallinity about 92%, and this black slag crystallite stone material is grey black, overall fracture, exquisite in texture.
Embodiment five
The color and luster of black slag crystallite stone material, fracture, texture and the physical properties (principal crystalline phase, degree of crystallinity) thereof prepare embodiment one-embodiment four and physicals (flexural strength) carry out the test of routine, and test result is as shown in table 1.
Note: the Performance Detection of (1) black slag crystallite stone material is tested according to standard JC/T872-2000 " Expectation of Glass-Ceramics Used as Decorated Materials " standard.
(2) principal crystalline phase, the degree of crystallinity employing XRD detection method of black slag crystallite stone material.
Table 1
As can be seen from Table 1, black slag microlite material pure color prepared by the embodiment of the present invention, fracture planeness is high, degree of crystallinity is high, and stone texture is given prominence to, excellent strength.
To sum up, it is high that the embodiment of the present invention prepares blast furnace utilization ratio in the raw material of black slag crystallite stone material, effectively can solve the problem that in current blast furnace slag black slag crystallite stone material, blast furnace slag addition is little, utilization ratio is low.Floating process is applied to preparation by the embodiment of the present invention is in addition in the black slag crystallite stone material field of main raw material with blast furnace slag, efficiently solves the technical problems such as the shaping difficulty that existing preparation technology causes due to short, the easy crystallization of high calcium glass melt material property is large, material road blocking.The black slag microlite material pure color simultaneously obtained, planeness are high, surface quality, and added value is high, deeply favors by market.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of described claim.
Claims (10)
1. a preparation method for black slag crystallite stone material, is characterized in that, comprise the steps:
By the mixture that the auxiliary material of the blast furnace slag of 60-80 weight part and 19-47 weight part is formed, carry out founding process and obtain glass melt; Wherein, the auxiliary material of described 19-47 weight part comprises: the reductive agent for providing the second adjusting material of sodium element, the Nucleating Agent of 4-10 weight part and 0-1 weight part for providing the first adjusting material of silicon-dioxide, 5-8 weight part of 10-28 weight part;
Described glass melt float glass process is shaped to glass board material;
Described glass board material is carried out coring, Crystallizing treatment obtains black slag crystallite stone material.
2. method according to claim 1, is characterized in that,
Described first adjusting material selects quartz sand;
Described second adjusting material selects sodium carbonate;
The Nucleating Agent of described 4-10 weight part comprises the Sodium Silicofluoride of the chromite of 2-4 weight part, the titanium dioxide of 0-1 weight part and 2-5 weight part;
Described reductive agent selects coal dust or carbon dust.
3. method according to claim 2, is characterized in that, described glass melt comprises following chemical composition: with weight, silicon-dioxide is 40-53%, calcium oxide is 20-30%, and aluminium sesquioxide is 9-13%, and magnesium oxide is 4-5.4%, ferric oxide is 1.2-2.2%, chromium sesquioxide is 1.2-2.5%, and sodium oxide is 3.4-5.8%, and fluorine is 1.2-3.4%, titanium dioxide is 0-1%, and surplus is inevitable impurity.
4. method according to claim 3, is characterized in that, described blast furnace slag is blast furnace water quenching slag;
Wherein, the described mixture formed by the auxiliary material that the blast furnace water of 60-80 weight part extraction quenches slag and 19-47 weight part, carries out founding process and obtains glass melt, be specially:
The blast furnace water quenching slag of 60-80 weight part is mixed with the auxiliary material of 19-47 weight part and obtains mixture;
Described mixture is fed in glass furnace, makes described mixture carry out melting at the temperature of 1450-1500 DEG C, homogenizing, obtain blend melt after clarification.
5. method according to claim 3, is characterized in that, described blast furnace slag is the hot melting slag of blast furnace;
Wherein, the mixture of the auxiliary material formation of the hot melting slag of the described blast furnace by 60-80 weight part and 19-47 weight part, carries out founding process and obtains glass melt, be specially:
Hot for the blast furnace of 60-80 weight part melting slag is introduced in glass furnace;
The auxiliary material of the 19-47 weight part mixed is fed in described glass furnace;
Make the hot melting slag of the blast furnace in described glass furnace mix formation mixture with described auxiliary material, make described mixture carry out melting at the temperature of 1450-1500 DEG C, homogenizing, obtain blend melt after clarification.
6. the method according to claim 4 or 5, is characterized in that, described step glass melt float glass process being shaped to glass board material is carried out in molten tin bath;
Wherein, the temperature of described molten tin bath polishing area is 1200-1075 DEG C, and the temperature of described molten tin bath cooling zone is 1050-650 DEG C.
7. method according to claim 6, is characterized in that, also comprises before described glass melt float glass process is shaped to the step of glass board material:
When the temperature of described glass melt is reduced to 1250-1300 DEG C, described glass melt is incorporated in described molten tin bath that to carry out float glass process shaping.
8. method according to claim 7, is characterized in that, the step obtaining black slag crystallite stone material after described glass board material is carried out coring, Crystallizing treatment is carried out in roller kiln, is specially:
Described glass board material is warming up to 690-750 DEG C through 30-60min, at 690-750 DEG C, is incubated 60-90min;
Described glass board material is warming up to 860-930 DEG C through 30-60min, at 860-930 DEG C, is incubated 60-90min;
Described glass board material is cooled to less than 80 DEG C through 90-120min, obtains black slag crystallite stone material.
9. a black slag crystallite stone material, is characterized in that, described black slag crystallite stone material is made up of the method described in any one of claim 1-8.
10. black slag crystallite stone material according to claim 9, is characterized in that, described black slag crystallite stone material comprises following chemical composition: with weight, silicon-dioxide is 40-50%, calcium oxide is 20-30%, and aluminium sesquioxide is 9-12%, and magnesium oxide is 4-5.3%, ferric oxide is 1.2-2.2%, chromium sesquioxide is 1.2-2.4%, and sodium oxide is 3.4-5.8%, and fluorine is 1.2-3.4%, titanium dioxide is 0-1%, and surplus is inevitable impurity.
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| CN106116158A (en) * | 2016-06-22 | 2016-11-16 | 河北省沙河玻璃技术研究院 | A kind of smelting cinder microcrystalline glass and preparation method thereof |
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| CN106517798A (en) * | 2016-10-21 | 2017-03-22 | 北京科技大学 | Method for preparing glass-ceramic by use of medium-low titanium type blast furnace slag |
| CN106746679A (en) * | 2016-12-15 | 2017-05-31 | 攀枝花环业冶金渣开发有限责任公司 | High-titanium blast furnace slag crystallite stone material and preparation method thereof |
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| CN106517798A (en) * | 2016-10-21 | 2017-03-22 | 北京科技大学 | Method for preparing glass-ceramic by use of medium-low titanium type blast furnace slag |
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