CN105481255B - With the method for utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass - Google Patents
With the method for utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass Download PDFInfo
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- CN105481255B CN105481255B CN201610029118.6A CN201610029118A CN105481255B CN 105481255 B CN105481255 B CN 105481255B CN 201610029118 A CN201610029118 A CN 201610029118A CN 105481255 B CN105481255 B CN 105481255B
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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
With the method for utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass, including preparing low-expansion glass-ceramic batch, low-expansion glass-ceramic batch includes the parts by weight of tailings of high silicon iron 40-45 of 80 mesh, the parts by weight of quartz sand 50-55 of 100 mesh, the parts by weight of aluminum oxide 10-15 of 100 mesh, the parts by weight of lithium carbonate 10-15, the parts by weight of zinc oxide 3-6, the parts by weight of barium selenate 3-6, the parts by weight of rare earth cerium oxide powder 2-5, the parts by weight of lithium zirconate 1-4, the parts by weight of boron nitride 2-5, the parts by weight of praseodymium chloride 3-6, the parts by weight of beryllium oxide 0.2-0.5, the parts by weight of basic bismuth carbonate 0.5-0.9, the parts by weight of sodium metaantimonate 0.1-0.4.Its object is to provide one kind to reduce environmental pollution, production cost is reduced, resulting devitrified glass thermal coefficient of expansion is low, heat endurance is high, softening temperature is high, the method for the extraordinary use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of thermal-shock resistance.
Description
Technical field
The present invention relates to a kind of method of use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass.
Background technology
Devitrified glass is a kind of polycrystalline material obtained from by controlling the crystallization of glass.Low-expansion glass-ceramic is mainly
Refer to Li2O-Al2O3-SiO2 system glass ceramics.Because it has been provided simultaneously with resisting temperature impact, high-frequency insulation, high mechanical properties,
The premium properties of this four aspects of high chemical stability, thus can be widely applied for astronomical telescope, high temperature electric light source glass,
Use for laboratory heats utensil, high-temperature heat exchanger, for fields such as quartz glass, window pyrometer, cooker, tablewares, has turned at present micro-
An important branch in crystal glass or even material science.
Existing devitrified glass is manufactured using a variety of chemical industry, and can not be effectively high using mine solid waste
Ferrosilicon mine tailing.Tailings of high silicon iron is a kind of mine solid waste, and it occupies arable land, pollution environment, and bulk deposition is it could even be possible to make
Into the disastrous accident of the threat to life property such as dam break, and its volume of cargo in storage can be reduced by being used as the raw material of industry,
Mitigate harm of the tailings of high silicon iron to environment.
The content of the invention
Mine solid waste tailings of high silicon iron is turned waste into wealth as primary raw material it is an object of the invention to provide one kind,
The comprehensive utilization of waste is realized, environmental pollution is reduced, production cost is reduced, resulting devitrified glass thermal coefficient of expansion is low, heat
Stability is high, and softening temperature is high, the method for the extraordinary use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of thermal-shock resistance.
The present invention makes a kind of useful construction material by effective processing to tailings of high silicon iron, provides simultaneously
A kind of effective approach for solving tailings of high silicon iron, forms a kind of benign cycle.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, it comprises the following steps：
A, preparation low-expansion glass-ceramic batch, low-expansion glass-ceramic batch include the tailings of high silicon iron of 80 mesh
40-45 parts by weight, the parts by weight of quartz sand 50-55 of 100 mesh, the parts by weight of aluminum oxide 10-15 of 100 mesh, lithium carbonate 10-15
Parts by weight, the parts by weight of zinc oxide 3-6, the parts by weight of barium selenate 3-6, the parts by weight of rare earth cerium oxide powder 2-5, lithium zirconate 1-4
Parts by weight, the parts by weight of boron nitride 2-5, the parts by weight of praseodymium chloride 3-6, the parts by weight of beryllium oxide 0.2-0.5, basic bismuth carbonate 0.5-
0.9 parts by weight, the parts by weight of sodium metaantimonate 0.1-0.4；
The weight percent composition of the tailings of high silicon iron is：Silica 69.08% -75.56%, aluminum oxide
1.93% -2.75%, di-iron trioxide 12.38% -18.46%, calcium oxide 3.52% -4.27%, magnesia 3.60% -
4.02% and 0.83% -1.97% various other compounds；
B, the glass batch for obtaining step A stir after mixing, then glass batch are placed in into cell furnace, earthenware
1500 DEG C~1530 DEG C are heated in crucible or cabinet-type electric furnace, glass batch is fused into liquid, 2-3 hours are incubated, then will
The glass metal of fusing is molded by the method for cast, compacting or calendering；
C, the obtained formed glasses of step B are immediately fed into kiln and annealed, temperature is 640 DEG C -650 DEG C, annealing
Time is 70-80 minutes；
D, carrying out coring processing immediately to the annealed glass that step C is obtained, coring treatment temperature is 715 DEG C -725 DEG C, core
It is 70-80 minutes to change processing time；
E, carry out Crystallizing treatment immediately to the glass that step D is obtained, Crystallizing treatment temperature is 880-890 DEG C, the time 70-
80 minutes；Crystallizing treatment terminates relief glass and is cooled to 650 DEG C with 2 DEG C -3 DEG C/h of speed, then with 6 DEG C -8 DEG C/h
Speed be cooled to room temperature, you can obtain low-expansion glass-ceramic.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, wherein low bulk is micro- in the step A
Crystal glass batch includes the parts by weight of tailings of high silicon iron 41-44, the parts by weight of quartz sand 51-54 of 100 mesh, 100 mesh of 80 mesh
Parts by weight of aluminum oxide 11-14, parts by weight of lithium carbonate 11-14, the parts by weight of zinc oxide 4-5, the parts by weight of barium selenate 4-5, dilute
The native parts by weight of cerium oxide powder 3-4, the parts by weight of lithium zirconate 2-3, the parts by weight of boron nitride 3-4, the parts by weight of praseodymium chloride 4-5, oxygen
Change the parts by weight of beryllium 0.3-0.4, the parts by weight of basic bismuth carbonate 0.6-0.8, the parts by weight of sodium metaantimonate 0.2-0.3.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, wherein being by glass in the step B
Batch, which is placed in cell furnace, crucible or cabinet-type electric furnace, is heated to 1510 DEG C~1520 DEG C, glass batch is fused into liquid
State, is incubated 2.2-2.8 hours, is then molded the glass metal of fusing by the method for cast, compacting or calendering.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, wherein annealing temperature in the step C
For 642 DEG C-648 DEG C, annealing time is 72-78 minutes；Crystallizing treatment temperature is 882-888 DEG C, time in the step E
72-78 minutes.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, wherein low bulk is micro- in the step A
Crystal glass batch includes the parts by weight of tailings of high silicon iron 42-43, the parts by weight of quartz sand 52-53 of 100 mesh, 100 mesh of 80 mesh
The parts by weight of aluminum oxide 12-13, the parts by weight of lithium carbonate 12-13, the parts by weight of zinc oxide 4.5, the parts by weight of barium selenate 4.5, rare earth
The parts by weight of cerium oxide powder 3.5, the parts by weight of lithium zirconate 2.5, the parts by weight of boron nitride 3.5, the parts by weight of praseodymium chloride 4.5, beryllium oxide
0.35 parts by weight, the parts by weight of basic bismuth carbonate 0.7, the parts by weight of sodium metaantimonate 0.25.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, wherein being by glass in the step B
Batch, which is placed in cell furnace, crucible or cabinet-type electric furnace, is heated to 1515 DEG C~1518 DEG C, glass batch is fused into liquid
State, is incubated 2.5 hours, is then molded the glass metal of fusing by the method for cast, compacting or calendering.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, wherein annealing temperature in the step C
For 644 DEG C -646 DEG C, annealing time is 75 minutes；Crystallizing treatment temperature is 884-886 DEG C, 75 points of time in the step E
Clock.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, its glass batch includes the height of 80 mesh
The parts by weight of ferrosilicon mine tailing 40-45, the parts by weight of quartz sand 50-55 of 100 mesh, the parts by weight of aluminum oxide 10-15 of 100 mesh, carbonic acid
The parts by weight of lithium 10-15, the parts by weight of zinc oxide 3-6, the parts by weight of barium selenate 3-6, the parts by weight of rare earth cerium oxide powder 2-5, zirconium
The sour parts by weight of lithium 1-4, the parts by weight of boron nitride 2-5, the parts by weight of praseodymium chloride 3-6, the parts by weight of beryllium oxide 0.2-0.5, alkali formula carbon
The sour parts by weight of bismuth 0.5-0.9, the parts by weight of sodium metaantimonate 0.1-0.4；As a result of the exclusive formula of the present invention, greatly carry
The high heat-resisting quantity of glassware, significantly improves the heat endurance of glassware, reduces the thermal expansion system of glassware
Number, also effectively increases the mechanical strength of glassware, the thermal coefficient of expansion of glassware is 1.5 × 10-7/ DEG C, bending strength
150Mpa is can reach, heat distortion temperature can reach more than 1300 DEG C.Therefore, use utilizing high-ferrosilicon tailings to manufacture low-expansion of the invention is micro-
The method of crystal glass has prominent substantive distinguishing features and significant progress.
It is described further with reference to the present invention with the method for utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass.
Embodiment
Embodiment 1
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, comprises the following steps：
A, preparation low-expansion glass-ceramic batch, low-expansion glass-ceramic batch include the tailings of high silicon iron of 80 mesh
40-45 parts by weight, the parts by weight of quartz sand 50-55 of 100 mesh, the parts by weight of aluminum oxide 10-15 of 100 mesh, lithium carbonate 10-15
Parts by weight, the parts by weight of zinc oxide 3-6, the parts by weight of barium selenate 3-6, the parts by weight of rare earth cerium oxide powder 2-5, lithium zirconate 1-4
Parts by weight, the parts by weight of boron nitride 2-5, the parts by weight of praseodymium chloride 3-6, the parts by weight of beryllium oxide 0.2-0.5, basic bismuth carbonate 0.5-
0.9 parts by weight, the parts by weight of sodium metaantimonate 0.1-0.4；
The weight percent composition of the tailings of high silicon iron is：Silica 69.08% -75.56%, aluminum oxide
1.93% -2.75%, di-iron trioxide 12.38% -18.46%, calcium oxide 3.52% -4.27%, magnesia 3.60% -
4.02% and 0.83% -1.97% various other compounds；Various other compounds can be considered impurity；
B, the glass batch for obtaining step A stir after mixing, then glass batch are placed in into cell furnace, earthenware
1500 DEG C~1530 DEG C are heated in crucible or cabinet-type electric furnace, glass batch is fused into liquid, 2-3 hours are incubated, then will
The glass metal of fusing is molded by the method for cast, compacting or calendering；
C, the obtained formed glasses of step B are immediately fed into kiln and annealed, temperature is 640 DEG C -650 DEG C, annealing
Time is 70-80 minutes；
D, carrying out coring processing immediately to the annealed glass that step C is obtained, coring treatment temperature is 715 DEG C -725 DEG C, core
It is 70-80 minutes to change processing time；
E, carry out Crystallizing treatment immediately to the glass that step D is obtained, Crystallizing treatment temperature is 880-890 DEG C, the time 70-
80 minutes；Crystallizing treatment terminates relief glass and is cooled to 650 DEG C with 2 DEG C -3 DEG C/h of speed, then with 6 DEG C -8 DEG C/h
Speed be cooled to room temperature, you can obtain low-expansion glass-ceramic.
As a further improvement on the present invention, low-expansion glass-ceramic batch includes the high silicon of 80 mesh in above-mentioned steps A
The parts by weight of iron tailings 41-44, the parts by weight of quartz sand 51-54 of 100 mesh, the parts by weight of aluminum oxide 11-14 of 100 mesh, lithium carbonate
11-14 parts by weight, the parts by weight of zinc oxide 4-5, the parts by weight of barium selenate 4-5, the parts by weight of rare earth cerium oxide powder 3-4, zirconic acid
The parts by weight of lithium 2-3, the parts by weight of boron nitride 3-4, the parts by weight of praseodymium chloride 4-5, the parts by weight of beryllium oxide 0.3-0.4, basic carbonate
The parts by weight of bismuth 0.6-0.8, the parts by weight of sodium metaantimonate 0.2-0.3.
As a further improvement on the present invention, it is that glass batch is placed in cell furnace, crucible or case in above-mentioned steps B
1510 DEG C~1520 DEG C are heated in formula electric furnace, glass batch is fused into liquid, 2.2-2.8 hours are incubated, then will be molten
The glass metal of change is molded by the method for cast, compacting or calendering.
As a further improvement on the present invention, annealing temperature is 642 DEG C -648 DEG C in above-mentioned steps C, and annealing time is
72-78 minutes；Crystallizing treatment temperature is 882-888 DEG C, 72-78 minutes time in the step E.
As a further improvement on the present invention, low-expansion glass-ceramic batch includes the high silicon of 80 mesh in above-mentioned steps A
The parts by weight of iron tailings 42-43, the parts by weight of quartz sand 52-53 of 100 mesh, the parts by weight of aluminum oxide 12-13 of 100 mesh, lithium carbonate
12-13 parts by weight, the parts by weight of zinc oxide 4.5, the parts by weight of barium selenate 4.5, the parts by weight of rare earth cerium oxide powder 3.5, lithium zirconate
2.5 parts by weight, the parts by weight of boron nitride 3.5, the parts by weight of praseodymium chloride 4.5, the parts by weight of beryllium oxide 0.35, the weight of basic bismuth carbonate 0.7
Part, the parts by weight of sodium metaantimonate 0.25.
As a further improvement on the present invention, it is that glass batch is placed in cell furnace, crucible or case in above-mentioned steps B
1515 DEG C~1518 DEG C are heated in formula electric furnace, glass batch is fused into liquid, 2.5 hours are incubated, then by fusing
Glass metal is molded by the method for cast, compacting or calendering.
As a further improvement on the present invention, annealing temperature is 644 DEG C -646 DEG C in above-mentioned steps C, and annealing time is 75
Minute；Crystallizing treatment temperature is 884-886 DEG C, 75 minutes time in the step E.
The method of the use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass of the present invention, due to being utilized because tailings of high silicon iron
As raw material, it is used in glass batch and replaces part quartz sand, aluminum oxide, magnesia, soda ash, potassium carbonate etc. conventional former
Material, can reduce glass batch cost more than 30%, and can reduce environmental pollution.Present invention system is determined using three-point bending method
The low-expansion glass-ceramic made, its bending strength can reach more than 150MPa, test produced by the present invention low using thermal dilatometer
Expansion devitrified glass, its thermal coefficient of expansion is only 1.5 × 10-7/℃。
Claims (7)
1. with the method for utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass, it is characterised in that comprise the following steps：
A, preparation low-expansion glass-ceramic batch, low-expansion glass-ceramic batch include the tailings of high silicon iron 40-45 of 80 mesh
Parts by weight, the parts by weight of quartz sand 50-55 of 100 mesh, the parts by weight of aluminum oxide 10-15 of 100 mesh, the weight of lithium carbonate 10-15
Part, the parts by weight of zinc oxide 3-6, the parts by weight of barium selenate 3-6, the parts by weight of rare earth cerium oxide powder 2-5, the weight of lithium zirconate 1-4
Part, the parts by weight of boron nitride 2-5, the parts by weight of praseodymium chloride 3-6, the parts by weight of beryllium oxide 0.2-0.5, basic bismuth carbonate 0.5-0.9
Parts by weight, the parts by weight of sodium metaantimonate 0.1-0.4；
The weight percent composition of the tailings of high silicon iron is：Silica 69.08% -75.56%, aluminum oxide 1.93% -
2.75%th, di-iron trioxide 12.38% -18.46%, calcium oxide 3.52% -4.27%, magnesia 3.60% -4.02% and
0.83% -1.97% various other compounds；
B, the glass batch for obtaining step A stir after mixing, then by glass batch be placed in cell furnace, crucible or
1500 DEG C~1530 DEG C are heated in cabinet-type electric furnace, glass batch is fused into liquid, 2-3 hours are incubated, then will fusing
Glass metal pass through cast, compacting or calendering method be molded；
C, the obtained formed glasses of step B being immediately fed into kiln and annealed, temperature is 640 DEG C -650 DEG C, annealing time
For 70-80 minutes；
D, carry out coring processing immediately to the annealed glass that step C is obtained, coring treatment temperature is 715 DEG C -725 DEG C, at coring
The reason time is 70-80 minutes；
E, carry out Crystallizing treatment immediately to the glass that step D is obtained, Crystallizing treatment temperature is 880-890 DEG C, 70-80 points of time
Clock；Crystallizing treatment terminates relief glass and is cooled to 650 DEG C with 2 DEG C -3 DEG C/h of speed, then with 6 DEG C -8 DEG C/h of speed
Degree is cooled to room temperature, you can obtain low-expansion glass-ceramic.
2. the method for use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass according to claim 1, it is characterised in that：It is described
Parts by weight of tailings of high silicon iron 41-44 of low-expansion glass-ceramic batch including 80 mesh in step A, 100 mesh quartz sand 51-
54 parts by weight, the parts by weight of aluminum oxide 11-14 of 100 mesh, the parts by weight of lithium carbonate 11-14, the parts by weight of zinc oxide 4-5, barium selenate
4-5 parts by weight, the parts by weight of rare earth cerium oxide powder 3-4, the parts by weight of lithium zirconate 2-3, the parts by weight of boron nitride 3-4, praseodymium chloride
4-5 parts by weight, the parts by weight of beryllium oxide 0.3-0.4, the parts by weight of basic bismuth carbonate 0.6-0.8, the weight of sodium metaantimonate 0.2-0.3
Part.
3. the method for use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass according to claim 2, it is characterised in that：It is described
It is that glass batch is placed in cell furnace, crucible or cabinet-type electric furnace to be heated to 1510 DEG C~1520 DEG C in step B, makes glass
Batch melting is incubated 2.2-2.8 hours into liquid, then by method of the glass metal of fusing by cast, compacting or calendering
Shaping.
4. the method for use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass according to claim 3, it is characterised in that：It is described
Annealing temperature is 642 DEG C-648 DEG C in step C, and annealing time is 72-78 minutes；Crystallizing treatment temperature is in the step E
882-888 DEG C, 72-78 minutes time.
5. the method for use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass according to claim 4, it is characterised in that：It is described
Parts by weight of tailings of high silicon iron 42-43 of low-expansion glass-ceramic batch including 80 mesh in step A, 100 mesh quartz sand 52-
53 parts by weight, the parts by weight of aluminum oxide 12-13 of 100 mesh, the parts by weight of lithium carbonate 12-13, the parts by weight of zinc oxide 4.5, barium selenate
4.5 parts by weight, the parts by weight of rare earth cerium oxide powder 3.5, the parts by weight of lithium zirconate 2.5, the parts by weight of boron nitride 3.5, the weight of praseodymium chloride 4.5
Measure part, the parts by weight of beryllium oxide 0.35, the parts by weight of basic bismuth carbonate 0.7, the parts by weight of sodium metaantimonate 0.25.
6. the method for use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass according to claim 5, it is characterised in that：It is described
It is that glass batch is placed in cell furnace, crucible or cabinet-type electric furnace to be heated to 1515 DEG C~1518 DEG C in step B, makes glass
Batch melting is incubated 2.5 hours into liquid, is then molded the glass metal of fusing by the method for cast, compacting or calendering.
7. the method for use utilizing high-ferrosilicon tailings to manufacture low-expansion microcrystalline glass according to claim 6, it is characterised in that：It is described
Annealing temperature is 644 DEG C -646 DEG C in step C, and annealing time is 75 minutes；Crystallizing treatment temperature is 884- in the step E
886 DEG C, 75 minutes time.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817640A (en) * | 2009-01-24 | 2010-09-01 | 北京清迈信息材料有限公司 | Method for manufacturing microlite by using high-silicon iron tailings |
| CN102229468A (en) * | 2010-07-09 | 2011-11-02 | 鞍钢集团矿业公司 | Low-expansion micro-crystal glass manufactured from high-silicon iron tailings and preparation method thereof |
| CN104016589A (en) * | 2014-06-27 | 2014-09-03 | 北京国泰珝天科技有限公司 | Iron tailing microcrystalline glass and preparation method thereof |
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| JP2775525B2 (en) * | 1990-12-25 | 1998-07-16 | 月島機械株式会社 | Method for producing crystallized glass |
| KR100683834B1 (en) * | 2005-12-30 | 2007-02-15 | 경기대학교 산학협력단 | Manufacturing method of glass-ceramics using steel dust in furnace |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817640A (en) * | 2009-01-24 | 2010-09-01 | 北京清迈信息材料有限公司 | Method for manufacturing microlite by using high-silicon iron tailings |
| CN102229468A (en) * | 2010-07-09 | 2011-11-02 | 鞍钢集团矿业公司 | Low-expansion micro-crystal glass manufactured from high-silicon iron tailings and preparation method thereof |
| CN104016589A (en) * | 2014-06-27 | 2014-09-03 | 北京国泰珝天科技有限公司 | Iron tailing microcrystalline glass and preparation method thereof |
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