CN110482865A - A kind of devitrified glass and preparation method thereof and purposes - Google Patents
A kind of devitrified glass and preparation method thereof and purposes Download PDFInfo
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- CN110482865A CN110482865A CN201910893892.5A CN201910893892A CN110482865A CN 110482865 A CN110482865 A CN 110482865A CN 201910893892 A CN201910893892 A CN 201910893892A CN 110482865 A CN110482865 A CN 110482865A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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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
- C03C10/0036—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 SiO2, Al2O3 and a divalent metal oxide as main constituents
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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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Abstract
The present invention relates to a kind of devitrified glass and preparation method thereof and purposes, the raw material of the devitrified glass is by percentage to the quality, the sum of mass percent of the ingredient of smelting industrial silicon waste residue and 15-50% including 50-85%, smelting industrial silicon waste residue and ingredient is 100%；Ingredient includes the combination of any one or at least two in auxiliary material, oxidant or clarifying agent；It include Si, Fe, Al, Ca, Mg, P, F, O, C and inevitable impurity in smelting industrial silicon waste residue.The present invention passes through addition auxiliary material, oxidant and clarifying agent, and pass through specific melt processed and Crystallizing treatment, form the crystal phase of gained devitrified glass by cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, flexural strength, compression strength, Mohs' hardness and wearability are high, acid resistance is good with alkali resistance, can be used as structural material and is widely used in the fields such as chemical industry, metallurgy, building decoration, petroleum, mine, machinery.
Description
Technical field
The invention belongs to Material Field, it is related to a kind of glass and the preparation method and application thereof more particularly to a kind of crystallite glass
Glass and preparation method thereof and purposes.
Background technique
Silicon industry is the basic former material of the important industry of non-ferrous metals industry, especially industrial silicon as entire silicon industry
Material, is constantly subjected to the extensive concern of domestic and international relevant industries in recent years.Smelting industrial silicon waste residue is production during industrial silicon production
A kind of raw smelted furnace cinder, silicon slag yield is about 1/10th of industrial silicon yield in industrial silicon production, and silicon slag is for a long time all
For paving the way or being stored up as waste, a large amount of soil space resource is occupied, 15% or more metal is usually contained in silicon slag
Silicon, these metallic silicons in the form of field trash preservation in silicon slag, it is difficult to separation and recovery utilize, cause the waste of resource.
106478364 A of CN discloses a kind of tribromoethane solution recovery device for silicon slag separation, including residue mould
Block and silicon module, the device improve fractionating effect, and cut point is controllable using repeatedly fractionation, and fractionating efficiency is high.CN
Convenient for the slag former and its application method of silicon slag separation, the slag making when 103342363 A disclose a kind of polycrystalline silicon medium melting
Agent and application method can be improved silicon slag separating effect, reduce silicon slag viscosity when silicon slag separation, improve the rate of recovery, reduce back
Harvest sheet.Qu Renjing (technique that industrial silicon is extracted from silicon slag, Yunnan metallurgy, 2012,41 (3): 83-85) provides a kind of place
The method for managing industrial silicon silicon slag is incorporated solvent, from industrial silicon using main frequency furnace by processes such as picking, machine choosing, ingredient, meltings
Elemental silicon is refined in waste, product reaches industrial silicon precision.The above method extracts silicon from silicon slag, but will also generate after separating useless
Slag, do not solve the problems, such as thoroughly smelting industrial silicon waste residue how resource utilization.
Devitrified glass is otherwise known as glass ceramics, is a kind of advanced composite material (ACM), has lower thermal expansion coefficient, higher
Mechanical strength, significant corrosion-resistant, weatherability, good thermal shock resistance, and the softening temperature of devitrified glass, heat
Stability, chemical stability, mechanical strength and hardness are above traditional glass, the uniform microstructure of devitrified glass is fine and close,
Pore-free, any surface finish, product size are accurate and can produce supersize product, with ceramic phase than with incomparable excellent
Gesture.
On the one hand, devitrified glass can substitute the traditional material of technical grade construction industry, can be used as structural material, optics material
The materials such as material, electricity material, construction material, and be widely used in national defence section work, machinery in mine, intelligence manufacture, environment-protecting industrial, build
The every field built and lived has huge application and prospect.On the other hand, devitrified glass solidification smelting industrial silicon is useless
Harm element in slag has to solidify and stablizes, endangers the advantage that element is difficult to dissolve out, and can effectively avoid and endangers element dissolution generation
The risk of secondary pollution.
103539357 A of CN discloses a kind of devitrified glass and preparation method thereof, and the devitrified glass is to smelt polysilicon production
Raw silicon slag is primary raw material, has developed novel SiO2-CaO-Na2O-K2O-ZnO-Al2O3-F、Na2O-CaO-SiO2-Al2O3-
ZnO、SiO2-CaO-ZnO-Al2O3-Na2O-BaO-K2O parent glass system, based on cuspidine, wollastonite, fluorine alkali wollastonite
The devitrified glass of crystal phase is wanted, and passes through the Fe in smelting silicon waste residue2O3、Al2O3Etc. micro constitutents regulation devitrified glass knot of tissue
Structure, optimization physical and mechanical property and chemical stability.But silicon slag used in this method is refining slag, and the Si in silicon slag is mainly with SiO2
Form exist, method disclosed in 103342363 A of Yi Caiyong CN 106478364 A or CN is to SiO therein2It is recycled
It utilizes.
Summary of the invention
The purpose of the present invention is to provide a kind of devitrified glass and preparation method thereof and purposes, the present invention passes through control crystallite
The raw material of glass forms, and parameter when preparing devitrified glass, makes the crystal phase of gained devitrified glass by cacoclasite, alkali silicon
Calcium stone, albite, cuspidine and diopside form, gained devitrified glass High anti bending strength, compression strength are high, mode hardness is high,
Wearability is high, can be used as structural material and is widely used in the fields such as chemical industry, metallurgy, building decoration, petroleum, mine, machinery.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
In a first aspect, the raw material of the devitrified glass by percentage to the quality, wraps the present invention provides a kind of devitrified glass
Include the smelting industrial silicon waste residue of 50-85% and the ingredient of 15-50%, the mass percent of the smelting industrial silicon waste residue and ingredient
The sum of be 100%.
The ingredient includes auxiliary material, oxidant and clarifying agent.
It include Si, Fe, Al, Ca, Mg, P, F, O, C and inevitable impurity in the smelting industrial silicon waste residue.
In smelting industrial silicon waste residue used in the present invention containing Si, Fe, Al, Ca, Mg, P, F, O, C and inevitably it is miscellaneous
Matter, by matching smelting industrial silicon waste residue with auxiliary material, oxidant, clarifying agent, providing components system is CaO-
Al2O3-SiO2The crystalline phase distribution of the devitrified glass of-MgO, gained devitrified glass is uniform, to improve the anti-of gained devitrified glass
Roll over intensity, compression strength, Mohs' hardness and wearability.
Preferably, the raw material of the devitrified glass includes smelting industrial silicon waste residue and ingredient, the smelting industrial silicon waste residue
It is 100% with the sum of the mass percent of ingredient, wherein the mass percent of smelting industrial silicon waste residue is 50-85%, such as can
To be 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, the mass percent of ingredient is 15-50%, such as can
To be 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range.
Preferably, the silicon in the smelting industrial silicon waste residue exists in the form of elemental silicon, silicon carbide and silica.
Preferably, the mass ratio (5-30) of the elemental silicon, silicon carbide and silica: (5-20): (20-60), example
Such as can be 5:5:20,5:10:20,5:15:20,5:20:20,10:5:30,15:10:40,20:15:50,25:10:60 or
30:20:60, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, in the smelting industrial silicon waste residue Si, Fe, Al, Ca, Mg, P, F, O and C mass ratio (30-40):
(0.1-0.2): (6-12): (10-25): (0.05-0.2): (0.01-0.08): (0-10): (20-40): (1-10), such as can
To be 30:0.1:6:10:0.05:0.01:0.01:20:1,32:0.12:8:12:0.1:0.03:2:25:3,34:0.15:9:
16:0.12:0.05:6:30:5,36:0.18:10:20:0.18:0.06:8:35:8 or 40:0.2:12:25:0.2:0.08:10:
40:10, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the crystal phase of the devitrified glass is by cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside
Composition.Devitrified glass provided by the invention is made by adding auxiliary material, oxidant and clarifying agent in smelting industrial silicon waste residue
The crystal form of devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, devitrified glass of the present invention
In cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside crystal phase mutually cooperate with, improve jointly gained it is micro-
Flexural strength, compression strength, Mohs' hardness and the wearability of crystal glass.
Preferably, the ingredient be auxiliary material, oxidant and clarifying agent combination, the auxiliary material, oxidant with
The mass ratio of clarifying agent is (62-95): (4-14): (1-11), such as can be 62:4:1,70:6:4,75:10:5,80:12:8
Or 85:14:11, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably
For (70-85): (6-12): (4-8).
Preferably, the auxiliary material includes at least three in quartz sand, calcite, soda ash, fluorite, magnesia or aluminium oxide
The combination of kind, typical but non-limiting combination include the combination of quartz sand, calcite and soda ash, calcite, soda ash and fluorite
Combination, the combination of soda ash, fluorite and magnesia, the combination of fluorite, magnesia and aluminium oxide, quartz sand, calcite, soda ash with
The combination of fluorite, calcite, soda ash, fluorite, magnesia and aluminium oxide combination or quartz sand, calcite, soda ash, fluorite, oxygen
Change the combination of magnesium and aluminium oxide, the preferably combination of quartz sand, calcite, soda ash, fluorite, magnesia and aluminium oxide.
Preferably, the mass ratio of the quartz sand, calcite, soda ash, fluorite, magnesia and aluminium oxide is (15-20):
(14-17): (5-8): (1-3): (0-2): (0-2), such as can be 15:14:5:1:0.1:0.1,16:15:6:1.5:0.5:
0.5,17:16:7:2:1:1,18:17:7.5:2.5:1.5:1.5 or 20:17:8:3:2:2.
Preferably, the oxidant includes any one in sodium nitrate, potassium nitrate, barium nitrate, cerous nitrate or nitric acid antimony
Or at least two combination, typical but non-limiting combination includes the combination of sodium nitrate and potassium nitrate, sodium nitrate and barium nitrate
Combination, the combination of potassium nitrate and cerous nitrate, the combination of cerous nitrate and nitric acid antimony, the combination of sodium nitrate, potassium nitrate and barium nitrate,
The combination of sodium nitrate, potassium nitrate and cerous nitrate, sodium nitrate, the combination of potassium nitrate and nitric acid antimony or sodium nitrate, potassium nitrate, nitric acid
The combination of barium, cerous nitrate and nitric acid antimony, preferably sodium nitrate, the combination of potassium nitrate, barium nitrate, cerous nitrate and nitric acid antimony.
The present invention is aoxidized the elemental silicon in smelting industrial silicon waste residue, by the addition of oxidant to make industrial silicon smelting
Refining waste residue can melt completely, and when fusing obtains homogeneous melt.
Preferably, the mass ratio of the sodium nitrate, potassium nitrate, barium nitrate, cerous nitrate and nitric acid antimony is (1-3): (0.1-
2): (0.1-3): (0.1-4): (0.1-5), such as can be 1:0.1:0.1:0.1:0.1,1:0.5:1.5:2:0.1,1.5:
0.5:0.5:0.5:0.5,2:1:1.5:2:2,2.5:1.5:2:2.5:3 or 3:2:3:4:5, it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable.
When the mass ratio of sodium nitrate, potassium nitrate, barium nitrate, cerous nitrate and nitric acid antimony is at (1-3): (0.1-2): (0.1-3):
(0.1-4): it when in (0.1-5) range, is mutually cooperateed between sodium nitrate, potassium nitrate, barium nitrate, cerous nitrate and nitric acid antimony, not only
It is capable of providing the nitrate ion of oxidation, sodium ion, potassium ion, barium ions, cerium ion and antimony ion can also be with industry
Other ions in silicon melting waste slag, auxiliary material and clarifying agent are compounded to form crystallite phase, improve the physical and chemical matter of devitrified glass
Amount.
Preferably, the clarifying agent includes any one in sodium sulphate, calcirm-fluoride, prodan, sodium antimonate or ammonium nitrate
Kind or at least two combination, typical but non-limiting combination includes the combination of sodium sulphate and calcirm-fluoride, sodium sulphate and fluorine silicon
The combination of the combination of the combination of the combination of sour sodium, sodium sulphate and sodium antimonate, sodium sulphate and ammonium nitrate, calcirm-fluoride and prodan,
The combination of the combination of calcirm-fluoride and sodium antimonate, prodan and ammonium nitrate, the combination of sodium sulphate, calcirm-fluoride and sodium antimonate, sulfuric acid
The combination of sodium, prodan and ammonium nitrate, the combination of sodium sulphate, calcirm-fluoride, sodium antimonate and ammonium nitrate, sodium sulphate, calcirm-fluoride, fluorine
The combination of sodium metasilicate and ammonium nitrate or the combination of sodium sulphate, calcirm-fluoride, prodan, sodium antimonate and ammonium nitrate, preferably sulfuric acid
The combination of sodium, calcirm-fluoride, prodan, sodium antimonate and ammonium nitrate.
Preferably, the mass ratio of the sodium sulphate, calcirm-fluoride, prodan, sodium antimonate and ammonium nitrate is (0.1-3):
(0.1-2): (1-3): (0.1-4): (0.1-5), such as can be 0.1:0.1:1:0.1:0.1,0.5:0.5:1.5:1:1,1:
1:2:1.5:2,1:1.5:2.5:3:2,1:2:3:4:2,2:1.5:2.5:2:3 or 3:2:3:4:5, it is not limited to cited
Numerical value, other unlisted numerical value are equally applicable in the numberical range.
Second aspect, the present invention provides a kind of method for preparing devitrified glass as described in relation to the first aspect, the methods
Include the following steps:
(1) formula ratio mixing smelting industrial silicon waste residue and ingredient, basis of formation batch are pressed；
(2) basic batch obtained by fusing step (1), clarification form glass metal after being homogenized；
(3) glass metal obtained by step (2) is cooled and shaped, obtains parent glass material；
(4) parent glass material obtained by Crystallizing treatment step (3), obtains the devitrified glass.
Preferably, described be molten at 1400-1500 DEG C of step (2) keeps the temperature 0.5-2h, then at 1550-1650 DEG C
Keep the temperature 0.5-5h.Fusion process of the present invention is divided into two sections, and wherein the temperature of first segment fusing is 1400-1500 DEG C, such as
It can be 1400 DEG C, 1420 DEG C, 1440 DEG C, 1460 DEG C, 1480 DEG C or 1500 DEG C, preferably 1420-1480 DEG C, first segment melts
Time be 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.8h or 2h, preferably 1-1.5h；The temperature of second segment fusing is 1550-
1650 DEG C, such as can be 1550 DEG C, 1560 DEG C, 1570 DEG C, 1580 DEG C, 1590 DEG C, 1600 DEG C, 1610 DEG C, 1620 DEG C, 1630
DEG C, 1640 DEG C or 1650 DEG C, preferably 1580-1620 DEG C, second segment fusing time be 0.5h, 1h, 1.5h, 2h, 2.5h,
3h, 3.5h, 4h, 4.5h or 5h, preferably 2-4h.
Preferably, the method for step (3) described cooling and shaping include casting, calendering or water quenching in any one or at least
Two kinds of combination.
Preferably, when the method for step (3) described cooling and shaping is casting and/or calendering, the temperature of cooling and shaping is 350
DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C or 650 DEG C, preferably 400-550 DEG C.
Casting, calendering and water quenching of the present invention are conventional technical means in the art, and the present invention is by burning note or calendering
Method obtain glass plate, glass grain is obtained by the method for water quenching, gained glass plate is crushed, glass blocks can be obtained.
Preferably, step (3) the parent glass material include in glass plate, glass blocks or glass grain any one or extremely
Few two kinds of combination, typical but non-limiting combination include the combination of glass plate and glass blocks, the group of glass plate and glass grain
It closes, glass blocks and the combination of glass grain or the combination of glass plate, glass blocks and glass grain.
Preferably, when step (3) the parent glass material is glass plate, the step of step (4) described Crystallizing treatment are as follows:
Glass plate at 350-650 DEG C, such as can be 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 400 DEG C, 420 DEG C, 450 DEG C,
480 DEG C, 500 DEG C, 550 DEG C, 600 DEG C or 600 DEG C, keep the temperature 1-6h, such as can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h,
4.5h, 5h, 5.5h or 6h；700-950 DEG C is then heated to, such as can be 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C or 900
DEG C, keep the temperature 1.5-9h, such as can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h,
7.5h, 8h, 8.5h or 9h；Then be cooled to 300-650 DEG C, for example, can be 300 DEG C, 320 DEG C, 350 DEG C, 380 DEG C, 400 DEG C,
420 DEG C, 450 DEG C, 480 DEG C, 500 DEG C, 540 DEG C, 560 DEG C, 600 DEG C or 650 DEG C, keep the temperature 2-8h, such as can be 2h, 2.5h,
3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h；50 DEG C are finally cooled to the furnace hereinafter, for example can be
15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C, obtain the devitrified glass.
Preferably, when step (3) the parent glass material is glass blocks and/or glass grain, at step (4) described crystallization
The step of reason are as follows: according to different granularity layered arrangement parent glass material, then heat to 1100-1200 DEG C, such as can be
1100 DEG C, 1110 DEG C, 1120 DEG C, 1130 DEG C, 1140 DEG C, 1150 DEG C, 1160 DEG C, 1170 DEG C, 1180 DEG C, 1190 DEG C or 1200
DEG C, and 0.5-2.5h is kept the temperature, such as can be 0.5h, 1h, 1.5h, 2h or 2.5h, shakeout surface；Then it is cooled to 300-500
DEG C, such as can be 300 DEG C, 320 DEG C, 340 DEG C, 360 DEG C, 380 DEG C, 400 DEG C, 420 DEG C, 440 DEG C, 460 DEG C, 480 DEG C or 500
DEG C, 1-6h is kept the temperature, such as can be 1h, 2h, 3h, 4h, 5h or 6h；Be warming up to 700-950 DEG C again, for example, can be 700 DEG C,
750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C or 950 DEG C, keep the temperature 1.5-9h, such as can be 1.5h, 2h, 2.5h, 3h, 3.5h, 4h,
4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h or 9h；Be cooled to 300-350 DEG C again, for example, can be 300 DEG C,
310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C or 350 DEG C, 2-8h is kept the temperature, such as can be 2h, 3h, 4h, 5h, 6h, 7h or 8h, finally
50 DEG C are cooled to the furnace hereinafter, for example can be 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C, obtains institute
State devitrified glass.
As the optimal technical scheme of second aspect of the present invention the method, described method includes following steps:
(1) formula ratio mixing smelting industrial silicon waste residue and ingredient, basis of formation batch are pressed；
(2) basic batch obtained by heating stepses (1) is to 1400-1500 DEG C, and keeps the temperature 0.5-2h, then in 1550-
0.5-5h is kept the temperature at 1650 DEG C, forms glass metal after clarification, homogenizing；
(3) glass metal obtained by step (2) is cooled and shaped, obtains parent glass material, the parent glass material includes glass
In plate, glass blocks or glass grain any one or at least two combination；
(4) parent glass material obtained by Crystallizing treatment step (3), obtains the devitrified glass, when parent glass material is glass
When plate, the step of step (4) described Crystallizing treatment are as follows: glass plate then heats to 700-950 in 350-650 DEG C of heat preservation 1-6h
DEG C, 1.5-9h is kept the temperature, is then cooled to 300-650 DEG C, 2-8h is kept the temperature, finally cools to 50 DEG C with the furnace hereinafter, obtaining described micro-
Crystal glass；
When parent glass material is glass blocks and/or glass grain, the step of step (4) described Crystallizing treatment are as follows: according to not
Same granularity layered arrangement parent glass material, then heats to 1100-1200 DEG C, and keep the temperature 0.5-2.5h, shakeouts surface, then
It is cooled to 300-500 DEG C, keeps the temperature 1-6h, then be warming up to 700-950 DEG C, keeps the temperature 1.5-9h, then be cooled to 300-350 DEG C, is kept the temperature
2-8h finally cools to 50 DEG C or less with the furnace.
" according to different granularity layered arrangement parent glass material " of the present invention be according to granularity from big to small, successively from
Bottom can make frit heated to high layer arrangement glass blocks and/or glass grain according to different granularity layered arrangement frits
Uniformly, to improve the quality of Crystallizing treatment.
The third aspect, the present invention provides the purposes that micro crystal material as described in relation to the first aspect is used for structural material.
Compared with the existing technology, the invention has the following advantages:
(1) present invention is using smelting industrial silicon waste residue as main material production devitrified glass, and wherein smelting industrial silicon waste residue exists
Amount in devitrified glass raw material can be adjusted in the range of 50-85wt%, and the full doseization for realizing smelting industrial silicon waste residue is comprehensive
It utilizes；
(2) occurrence patterns of the silicon in smelting industrial silicon waste residue are complicated, and the present invention in smelting industrial silicon waste residue by adding
Add specific oxidant, be components system is CaO-Al by the proportion of each ingredient in control oxidant2O3-SiO2The basis-MgO
Glass system provides a variety of cations, elemental silicon can not only be made to be oxidized to be fusible silica, moreover it is possible to make oxidant
In a variety of cations cooperatively form crystallite phase with other ions formation in components systems, to improve gained devitrified glass
Physical and chemical quality；
(3) component of glass is not easy into smelting industrial silicon waste residue of the present invention containing F, Mg etc., the present invention passes through addition
The ratio of each component when auxiliary material adjustment prepares devitrified glass, it is suppressed that at the spontaneous Crystallization Process during glass, thus
To metastable parent glass；
(4) present invention passes through the recycling of smelting industrial silicon waste residue, passes through glass phase, CaF2Etc. crystallite phases have cured F member
Element avoids secondary pollution caused by the dissolution of F element in smelting industrial silicon waste residue.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method for the devitrified glass that embodiment 1 provides.
Fig. 2 is the XRD spectra for the devitrified glass that embodiment 1 is prepared.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Smelting industrial silicon waste residue of the present invention includes cold conditions smelting industrial silicon waste residue and hot smelting industrial silicon waste residue, institute
Stating cold conditions smelting industrial silicon waste residue is the cold conditions slag that the hot smelting industrial silicon waste residue is cooled to room temperature lower formation.Industrial silicon smelting
Refining waste residue in silicon exists in the form of elemental silicon, silicon carbide and silica, and through measurement, elemental silicon, silicon carbide with
And the mass ratio of silica is at (5-30): (5-20): fluctuation in (20-60) range.
Contain Si, Fe, Al, Ca, Mg, P, F, O, C and inevitable impurity in the smelting industrial silicon waste residue, wherein
The mass ratio of Si, Fe, Al, Ca, Mg, P, F, O and C are at (30-40): (0.1-0.2): (6-12): (10-25): (0.05-
0.2): (0.01-0.08): (0-10): (20-40): being fluctuated in the range of (1-10).
Embodiment 1
A kind of preparation method of devitrified glass is present embodiments provided, the process flow chart of preparation method is as shown in Figure 1, packet
Include following steps:
(1) cold conditions smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 70wt%, and the mass fraction of ingredient is 30wt%；The auxiliary that ingredient is 78:9:6 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 18:16:6:2:1.5:1.5, calcite, pure
Alkali, fluorite, magnesia and aluminium oxide composition, sodium nitrate, potassium nitrate, the nitric acid that oxidant is 2:1:1.5:2:2 by mass ratio
Barium, cerous nitrate and nitric acid antimony form, and clarifying agent is by the sodium sulphate of mass ratio 1:1:2:2:2.5, calcirm-fluoride, prodan, metaantimmonic acid
Sodium and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1450 DEG C, and keeps the temperature 1.2h, then heats to
1600 DEG C, and 3h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is cast in the mold of preheating, is cooled and shaped at 450 DEG C, obtains basic glass
Glass plate；
(4) parent glass plate obtained by step (3) keeps the temperature 3h at 450 DEG C, then heats to 800 DEG C of heat preservation 5h, finally drops
Temperature finally cools to room temperature with the furnace, obtains the devitrified glass to 450 DEG C of heat preservation 5h.
The XRD spectra of gained devitrified glass is as shown in Fig. 2, cacoclasite (CaAl is precipitated in devitrified glass2Si2O8), alkali silicon
Calcium stone (Na4Ca4Si6O18), albite (NaAlSi3O8), cuspidine (Ca4Si2O7F2) and diopside (Ca (Mg, Al) (Al, Si)2O6) crystal phase composition, without obvious amorphous peak, the crystallinity of gained microcrystal glass plate is high.
The density of gained devitrified glass, Mohs' hardness, flexural strength and compression strength are carried out according to SN/T 0308-93
Test, is tested according to wearability of the JC/T 260-2001 to gained devitrified glass, according to JC/T 872-2000 to gained
The acid resistance of devitrified glass is tested with alkali resistance, acquired results are as follows: 2.70~2.75g/cm of density of the devitrified glass3,
6~8 grades of Mohs' hardness, flexural strength 90MPa, 0.060~0.065g/cm of wearability2, compression strength 560~570MPa is acidproof
Property 0.02%, alkali resistance 0.03%.
Embodiment 2
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) cold conditions smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 60wt%, and the mass fraction of ingredient is 40wt%；The auxiliary that ingredient is 70:6:4 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 15:14:5:1:1:1, calcite, soda ash, firefly
Stone, magnesia and aluminium oxide composition, sodium nitrate, potassium nitrate, the nitre that oxidant is 1.5:0.5:0.5:0.5:0.5 by mass ratio
Sour barium, cerous nitrate and nitric acid antimony form, clarifying agent by mass ratio 0.5:0.5:1.5:0.5:1 sodium sulphate, calcirm-fluoride, fluosilicic acid
Sodium, sodium antimonate and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1420 DEG C, and keeps the temperature 1.5h, then heats to
1580 DEG C, and 4h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is cast in the mold of preheating, is cooled and shaped at 400 DEG C, obtains basic glass
Glass plate；
(4) parent glass plate obtained by step (3) keeps the temperature 5h at 400 DEG C, then heats to 750 DEG C of heat preservation 6h, finally drops
Temperature finally cools to room temperature with the furnace, obtains the devitrified glass to 400 DEG C of heat preservation 6h.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Embodiment 3
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) hot smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 80wt%, and the mass fraction of ingredient is 20wt%；The auxiliary that ingredient is 85:12:8 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 20:17:8:3:2:2, calcite, soda ash, firefly
Stone, magnesia and aluminium oxide composition, sodium nitrate, potassium nitrate, the nitric acid that oxidant is 2.5:1.5:2.4:3:2.5 by mass ratio
Barium, cerous nitrate and nitric acid antimony form, and clarifying agent is by the sodium sulphate of mass ratio 2:1.5:2.5:3:4, calcirm-fluoride, prodan, antimony
Sour sodium and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1480 DEG C, and keeps the temperature 1h, then heats to 1620
DEG C, and 2h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is flowed through to roll calendar, is cooled and shaped at 550 DEG C, obtains parent glass
Plate；
(4) parent glass plate obtained by step (3) keeps the temperature 2h at 550 DEG C, then heats to 850 DEG C of heat preservation 3h, finally drops
Temperature finally cools to room temperature with the furnace, obtains the devitrified glass to 550 DEG C of heat preservation 3h.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Embodiment 4
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) hot smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 85wt%, and the mass fraction of ingredient is 15wt%；Ingredient is the auxiliary of 95:14:11 by mass ratio
Raw material, oxidant and clarifying agent is helped to form, auxiliary material is by the quartz sand of mass ratio 18:16:7:2:1.5:1.5, calcite, pure
Alkali, fluorite, magnesia and aluminium oxide composition, sodium nitrate, the nitric acid that oxidant is 1:0.1:0.1:0.1:0.1 by mass ratio
Potassium, barium nitrate, cerous nitrate and nitric acid antimony form, clarifying agent by the sodium sulphate of mass ratio 0.1:0.1:1:0.1:0.1, calcirm-fluoride,
Prodan, sodium antimonate and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1400 DEG C, and keeps the temperature 2h, then heats to 1550
DEG C, and 5h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is flowed through to roll calendar, is cooled and shaped at 650 DEG C, obtains parent glass
Plate；
(4) parent glass plate obtained by step (3) keeps the temperature 1h at 650 DEG C, then heats to 950 DEG C of heat preservation 1.5h, finally
650 DEG C of heat preservation 2h are cooled to, room temperature is finally cooled to the furnace, obtains the devitrified glass.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Embodiment 5
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) hot smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 50wt%, and the mass fraction of ingredient is 50wt%；The auxiliary that ingredient is 62:4:1 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 18:16:6:2:1.5:1.5, calcite, pure
Alkali, fluorite, magnesia and aluminium oxide composition, oxidant by mass ratio be the sodium nitrate of 3:2:3:4:5, potassium nitrate, barium nitrate,
Cerous nitrate and nitric acid antimony form, and clarifying agent is by the sodium sulphate of mass ratio 3:2:3:4:5, calcirm-fluoride, prodan, sodium antimonate and nitre
Sour ammonium composition；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1500 DEG C, and keeps the temperature 0.5h, then heats to
1650 DEG C, and 0.5h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is flowed through to roll calendar, is cooled and shaped at 350 DEG C, obtains parent glass
Plate；
(4) parent glass plate obtained by step (3) keeps the temperature 6h at 350 DEG C, then heats to 700 DEG C of heat preservation 9h, finally drops
Temperature finally cools to room temperature with the furnace, obtains the devitrified glass to 300 DEG C of heat preservation 8h.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Embodiment 6
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) cold conditions smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 70wt%, and the mass fraction of ingredient is 30wt%；The auxiliary that ingredient is 78:9:6 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 18:16:6:2:1.5:1.5, calcite, pure
Alkali, fluorite, magnesia and aluminium oxide composition, sodium nitrate, potassium nitrate, the nitric acid that oxidant is 2:1:1.5:2:2 by mass ratio
Barium, cerous nitrate and nitric acid antimony form, and clarifying agent is by the sodium sulphate of mass ratio 1:1:2:2:2.5, calcirm-fluoride, prodan, metaantimmonic acid
Sodium and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1450 DEG C, and keeps the temperature 1.2h, then heats to
1600 DEG C, and 3h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is poured into cold water, obtains the different glass grain of granularity after water quenching, drying；
(4) glass grain obtained by step (3) is arranged from bottom to high level according to the sequence of granularity from big to small, is then heated to
1150 DEG C, and 1.5h is kept the temperature, surface is shakeout, is then cooled to 400 DEG C, keeps the temperature 4h, then be warming up to 800 DEG C, keeps the temperature 5h, then cool down
To 320 DEG C, 5h is kept the temperature, room temperature is finally cooled to the furnace, obtains the devitrified glass.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Embodiment 7
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) hot smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 70wt%, and the mass fraction of ingredient is 30wt%；The auxiliary that ingredient is 78:9:6 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 18:16:6:2:1.5:1.5, calcite, pure
Alkali, fluorite, magnesia and aluminium oxide composition, sodium nitrate, potassium nitrate, the nitric acid that oxidant is 2:1:1.5:2:2 by mass ratio
Barium, cerous nitrate and nitric acid antimony form, and clarifying agent is by the sodium sulphate of mass ratio 1:1:2:2:2.5, calcirm-fluoride, prodan, metaantimmonic acid
Sodium and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1450 DEG C, and keeps the temperature 1.2h, then heats to
1600 DEG C, and 3h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is poured into cold water, obtains the different glass grain of granularity after water quenching, drying；
(4) glass grain obtained by step (3) is arranged from bottom to high level according to the sequence of granularity from big to small, is then heated to
1120 DEG C, and 2h is kept the temperature, surface is shakeout, is then cooled to 350 DEG C, keeps the temperature 5h, then be warming up to 750 DEG C, keeps the temperature 6h, then be cooled to
310 DEG C, 6h is kept the temperature, room temperature is finally cooled to the furnace, obtains the devitrified glass.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Embodiment 8
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) hot smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 70wt%, and the mass fraction of ingredient is 30wt%；The auxiliary that ingredient is 78:9:6 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 18:16:6:2:1.5:1.5, calcite, pure
Alkali, fluorite, magnesia and aluminium oxide composition, sodium nitrate, potassium nitrate, the nitric acid that oxidant is 2:1:1.5:2:2 by mass ratio
Barium, cerous nitrate and nitric acid antimony form, and clarifying agent is by the sodium sulphate of mass ratio 1:1:2:2:2.5, calcirm-fluoride, prodan, metaantimmonic acid
Sodium and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1450 DEG C, and keeps the temperature 1.2h, then heats to
1600 DEG C, and 3h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is cast in the mold of preheating, is cooled and shaped at 400 DEG C, and will obtained
Glass plate is broken into glass blocks；
(4) glass blocks obtained by step (3) is arranged from bottom to high level according to the sequence of granularity from big to small, is then heated to
1180 DEG C, and 1h is kept the temperature, surface is shakeout, is then cooled to 450 DEG C, keeps the temperature 2h, then be warming up to 850 DEG C, keeps the temperature 3h, then be cooled to
330 DEG C, 4h is kept the temperature, room temperature is finally cooled to the furnace, obtains the devitrified glass.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Embodiment 9
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) hot smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 70wt%, and the mass fraction of ingredient is 30wt%；The auxiliary that ingredient is 78:9:6 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 18:16:6:2:1.5:1.5, calcite, pure
Alkali, fluorite, magnesia and aluminium oxide composition, sodium nitrate, potassium nitrate, the nitric acid that oxidant is 2:1:1.5:2:2 by mass ratio
Barium, cerous nitrate and nitric acid antimony form, and clarifying agent is by the sodium sulphate of mass ratio 1:1:2:2:2.5, calcirm-fluoride, prodan, metaantimmonic acid
Sodium and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1450 DEG C, and keeps the temperature 1.2h, then heats to
1600 DEG C, and 3h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is poured into cold water, obtains the different glass grain of granularity after water quenching, drying；
(4) glass grain obtained by step (3) is arranged from bottom to high level according to the sequence of granularity from big to small, is then heated to
1100 DEG C, and 2.5h is kept the temperature, surface is shakeout, is then cooled to 300 DEG C, keeps the temperature 6h, then be warming up to 700 DEG C, keeps the temperature 9h, then cool down
To 300 DEG C, 8h is kept the temperature, room temperature is finally cooled to the furnace, obtains the devitrified glass.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Embodiment 10
A kind of preparation method of devitrified glass is present embodiments provided, described method includes following steps:
(1) hot smelting industrial silicon waste residue and ingredient are mixed, basis of formation batch, cold conditions industrial silicon in basic batch
The mass fraction of melting waste slag is 70wt%, and the mass fraction of ingredient is 30wt%；The auxiliary that ingredient is 78:9:6 by mass ratio
Raw material, oxidant and clarifying agent form, and auxiliary material is by the quartz sand of mass ratio 18:16:6:2:1.5:1.5, calcite, pure
Alkali, fluorite, magnesia and aluminium oxide composition, sodium nitrate, potassium nitrate, the nitric acid that oxidant is 2:1:1.5:2:2 by mass ratio
Barium, cerous nitrate and nitric acid antimony form, and clarifying agent is by the sodium sulphate of mass ratio 1:1:2:2:2.5, calcirm-fluoride, prodan, metaantimmonic acid
Sodium and ammonium nitrate form；
(2) basic batch obtained by heating stepses (1) makes its fusing to 1450 DEG C, and keeps the temperature 1.2h, then heats to
1600 DEG C, and 3h is kept the temperature, glass metal is formed after clarification, homogenizing；
(3) glass metal obtained by step (2) is poured into cold water, obtains the different glass grain of granularity after water quenching, drying；
(4) glass grain obtained by step (3) is arranged from bottom to high level according to the sequence of granularity from big to small, is then heated to
1200 DEG C, and 0.5h is kept the temperature, surface is shakeout, is then cooled to 500 DEG C, keeps the temperature 1h, then be warming up to 950 DEG C, keeps the temperature 1.5h, then drop
Temperature keeps the temperature 2h, finally cools to room temperature with the furnace, obtain the devitrified glass to 350 DEG C.
The crystal phase of gained devitrified glass is made of cacoclasite, alkali silicoglaserite, albite, cuspidine and diopside, institute
The crystallinity for obtaining microcrystal glass plate is high, and flexural strength, compression strength, Mohs' hardness and wearability are high, and acid resistance is good with alkali resistance.
Comparative example 1
This comparative example provides a kind of preparation method of devitrified glass, except step (1) ingredient is 78:6 by mass ratio
Auxiliary material and clarifying agent composition it is outer, remaining is same as Example 1.
Due to being not added with oxidant in comparative example 1, the elemental silicon in industrial silicon waste residue can not be aoxidized, therefore be unable to get
Devitrified glass.
In conclusion the present invention is using smelting industrial silicon waste residue as main material production devitrified glass, wherein smelting industrial silicon
Amount of the waste residue in devitrified glass raw material can be adjusted in the range of 50-85wt%, realize the full dose of smelting industrial silicon waste residue
Change comprehensive utilization；For the present invention by adding oxidant in smelting industrial silicon waste residue, having adjusted components system is CaO-Al2O3-
SiO2The oxidability of-MgO parent glass system, makes elemental silicon be oxidized to the silica that can be melted, moreover, the present invention is logical
Cross the ratio of addition auxiliary material adjustment each component when preparing devitrified glass, it is suppressed that at the spontaneous Crystallization Process during glass from
And the quality of gained devitrified glass is improved, make gained devitrified glass flexural strength, compression strength, Mohs' hardness and wearability
Height, acid resistance is good with alkali resistance, can be used as structural material and is widely used in chemical industry, metallurgy, building decoration, petroleum, mine, machinery
Equal fields.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of devitrified glass, which is characterized in that the raw material of the devitrified glass by percentage to the quality, including 50-85%'s
The ingredient of smelting industrial silicon waste residue and 15-50%, the sum of the smelting industrial silicon waste residue and the mass percent of ingredient are
100%；
The ingredient includes auxiliary material, oxidant and clarifying agent；
It include Si, Fe, Al, Ca, Mg, P, F, O, C and inevitable impurity in the smelting industrial silicon waste residue.
2. devitrified glass according to claim 1, which is characterized in that the silicon in the smelting industrial silicon waste residue is with simple substance
The form of silicon, silicon carbide and silica exists；
Preferably, the mass ratio (5-30) of the elemental silicon, silicon carbide and silica: (5-20): (20-60)；
Preferably, the mass ratio of Si, Fe, Al, Ca, Mg, P, F, O and C are (30-40) in the smelting industrial silicon waste residue:
(0.1-0.2):(6-12):(10-25):(0.05-0.2):(0.01-0.08):(0-10):(20-40):(1-10)。
3. devitrified glass according to claim 1 or 2, which is characterized in that the crystal phase of the devitrified glass is long by calcium aluminium Huang
Stone, alkali silicoglaserite, albite, cuspidine and diopside form.
4. devitrified glass according to claim 1-3, which is characterized in that the ingredient is auxiliary material, oxidation
The combination of agent and clarifying agent, the mass ratio of the auxiliary material, oxidant and clarifying agent are (62-95): (4-14): (1-11),
Preferably (70-85): (6-12): (4-8)；
Preferably, the auxiliary material includes at least three kinds in quartz sand, calcite, soda ash, fluorite, magnesia or aluminium oxide
Combination；
Preferably, the auxiliary material is the combination of quartz sand, calcite, soda ash, fluorite, magnesia and aluminium oxide；
Preferably, the mass ratio of the quartz sand, calcite, soda ash, fluorite, magnesia and aluminium oxide is (15-20): (14-
17):(5-8):(1-3):(0-2):(0-2)；
Preferably, the oxidant include in sodium nitrate, potassium nitrate, barium nitrate, cerous nitrate or nitric acid antimony any one or extremely
Few two kinds of combination, the preferably combination of sodium nitrate, potassium nitrate, barium nitrate, cerous nitrate and nitric acid antimony；
Preferably, the mass ratio of the sodium nitrate, potassium nitrate, barium nitrate, cerous nitrate and nitric acid antimony is (1-3): (0.1-2):
(0.1-3):(0.1-4):(0.1-5)；
Preferably, the clarifying agent include in sodium sulphate, calcirm-fluoride, prodan, sodium antimonate or ammonium nitrate any one or
At least two combination, preferably sodium sulphate, the combination of calcirm-fluoride, prodan, sodium antimonate and ammonium nitrate；
Preferably, the mass ratio of the sodium sulphate, calcirm-fluoride, prodan, sodium antimonate and ammonium nitrate is (0.1-3): (0.1-
2):(1-3):(0.1-4):(0.1-5)。
5. a kind of method for preparing the described in any item devitrified glasses of claim 1-4, which is characterized in that the method includes such as
Lower step:
(1) formula ratio mixing smelting industrial silicon waste residue and ingredient, basis of formation batch are pressed；
(2) basic batch obtained by fusing step (1), clarification form glass metal after being homogenized；
(3) glass metal obtained by step (2) is cooled and shaped, obtains parent glass material；
(4) parent glass material obtained by Crystallizing treatment step (3), obtains the devitrified glass.
6. according to the method described in claim 5, it is characterized in that, described be molten into of step (2) keeps the temperature at 1400-1500 DEG C
Then 0.5-2h keeps the temperature 0.5-5h at 1550-1650 DEG C；
Preferably, described be molten at 1420-1480 DEG C of step (2) keeps the temperature 1-1.5h, then keeps the temperature at 1580-1620 DEG C
2-4h。
7. method according to claim 5 or 6, which is characterized in that the method for step (3) described cooling and shaping includes pouring
Note, calendering or water quenching in any one or at least two combination；
Preferably, when the method for step (3) described cooling and shaping is casting and/or calendering, the temperature of cooling and shaping is 350-650
DEG C, preferably 400-550 DEG C.
8. according to the described in any item methods of claim 5-7, which is characterized in that step (3) the parent glass material includes glass
In glass plate, glass blocks or glass grain any one or at least two combination；
Preferably, when step (3) the parent glass material is glass plate, the step of step (4) described Crystallizing treatment are as follows: glass
Plate then heats to 700-950 DEG C in 350-650 DEG C of heat preservation 1-6h, keeps the temperature 1.5-9h, is then cooled to 300-650 DEG C, heat preservation
2-8h finally cools to 50 DEG C with the furnace hereinafter, obtaining the devitrified glass；
Preferably, when step (3) the parent glass material is glass blocks and/or glass grain, step (4) described Crystallizing treatment
Step are as follows: according to different granularity layered arrangement parent glass material, 1100-1200 DEG C is then heated to, and keep the temperature 0.5-2.5h,
Surface is shakeout, is then cooled to 300-500 DEG C, keeps the temperature 1-6h, then be warming up to 700-950 DEG C, keeps the temperature 1.5-9h, then be cooled to
300-350 DEG C, 2-8h is kept the temperature, finally cools to 50 DEG C or less with the furnace.
9. according to the described in any item methods of claim 5-8, which is characterized in that described method includes following steps:
(1) formula ratio mixing smelting industrial silicon waste residue and ingredient, basis of formation batch are pressed；
(2) basic batch obtained by heating stepses (1) is to 1400-1500 DEG C, and keeps the temperature 0.5-2h, then at 1550-1650 DEG C
Lower heat preservation 0.5-5h, clarification form glass metal after being homogenized；
(3) glass metal obtained by step (2) is cooled and shaped, obtains parent glass material, the parent glass material includes glass plate, glass
In glass block or glass grain any one or at least two combination；
(4) parent glass material obtained by Crystallizing treatment step (3), obtains the devitrified glass, when parent glass material is glass plate,
The step of step (4) described Crystallizing treatment are as follows: glass plate then heats to 700-950 DEG C in 350-650 DEG C of heat preservation 1-6h, protects
Then warm 1.5-9h is cooled to 300-650 DEG C, keep the temperature 2-8h, finally cool to 50 DEG C with the furnace hereinafter, obtaining the crystallite glass
Glass；
When parent glass material is glass blocks and/or glass grain, the step of step (4) described Crystallizing treatment are as follows: according to different
Granularity layered arrangement parent glass material, then heats to 1100-1200 DEG C, and keep the temperature 0.5-2.5h, shakeouts surface, then cool down
To 300-500 DEG C, 1-6h is kept the temperature, then be warming up to 700-950 DEG C, keeps the temperature 1.5-9h, then be cooled to 300-350 DEG C, keeps the temperature 2-8h,
Finally cool to 50 DEG C or less with the furnace.
10. the purposes that micro crystal material according to any one of claims 1-4 is used for structural material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910893892.5A CN110482865A (en) | 2019-09-20 | 2019-09-20 | A kind of devitrified glass and preparation method thereof and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910893892.5A CN110482865A (en) | 2019-09-20 | 2019-09-20 | A kind of devitrified glass and preparation method thereof and purposes |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111763010A (en) * | 2020-07-04 | 2020-10-13 | 上海和惠生态环境科技有限公司 | Method for preparing glass by melting solid waste at high temperature |
| CN112142333A (en) * | 2020-09-30 | 2020-12-29 | 中国科学院过程工程研究所 | Multi-source fluorine-containing waste residue microcrystalline glass solidified body and preparation method and application thereof |
| CN112851121A (en) * | 2021-01-18 | 2021-05-28 | 山东龙宇玻璃有限公司 | Method for promoting resource utilization of high-speed rail tailings by using silicon slag |
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| CN103539357A (en) * | 2013-08-27 | 2014-01-29 | 中国科学院过程工程研究所 | Silicon-slag microcrystalline glass and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763010A (en) * | 2020-07-04 | 2020-10-13 | 上海和惠生态环境科技有限公司 | Method for preparing glass by melting solid waste at high temperature |
| CN111763010B (en) * | 2020-07-04 | 2021-06-01 | 上海和惠生态环境科技有限公司 | Method for preparing glass by melting solid waste at high temperature |
| CN112142333A (en) * | 2020-09-30 | 2020-12-29 | 中国科学院过程工程研究所 | Multi-source fluorine-containing waste residue microcrystalline glass solidified body and preparation method and application thereof |
| CN112851121A (en) * | 2021-01-18 | 2021-05-28 | 山东龙宇玻璃有限公司 | Method for promoting resource utilization of high-speed rail tailings by using silicon slag |
| CN112851121B (en) * | 2021-01-18 | 2022-12-23 | 山东龙宇玻璃有限公司 | Method for promoting resource utilization of high-speed rail tailings by using silicon slag |
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