CN108395104A - It is the method that primary raw material prepares black glass ceramic new material using origin-state ash - Google Patents
It is the method that primary raw material prepares black glass ceramic new material using origin-state ash Download PDFInfo
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- CN108395104A CN108395104A CN201810321405.3A CN201810321405A CN108395104A CN 108395104 A CN108395104 A CN 108395104A CN 201810321405 A CN201810321405 A CN 201810321405A CN 108395104 A CN108395104 A CN 108395104A
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- 239000002994 raw material Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 32
- 238000002425 crystallisation Methods 0.000 claims abstract description 31
- 230000008025 crystallization Effects 0.000 claims abstract description 31
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000003490 calendering Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- 238000005352 clarification Methods 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000011265 semifinished product Substances 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 abstract description 14
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 6
- 239000002910 solid waste Substances 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241001237728 Precis Species 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 It is of low cost Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B13/00—Rolling molten glass, i.e. where the molten glass is shaped by rolling
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of methods preparing black glass ceramic new material using origin-state ash for primary raw material, include the following steps：Step 1: raw material selects；Step 2: raw material mixes；Step 3: the fusing of mixture；Step 4: calendaring molding；Step 5: annealing；Step 6: crystallization.Origin-state ash slag can make devitrified glass that black be presented containing a small amount of transition metal ions in the present invention, be not necessarily to additional colorant, can produce black glass ceramic, therefore raw material type is simple, facilitate production.The present invention can effectively solve the environmental hazard that waste residue is brought.
Description
Technical field
The present invention relates to a kind of preparation methods of devitrified glass, and in particular to a kind of to be prepared for primary raw material using origin-state ash
The method of black glass ceramic new material.
Background technology
Cinder microcrystalline glass is introduced a certain amount of using the industrial residues such as metallurgical slag, tailing and natural minerals as primary raw material
The auxiliary materials such as Nucleating Agent, fluxing agent, through a kind of crystallite material made of the processes such as dispensing, fusing, molding, annealing, crystallization
Material.With the quickening of China's process of industrialization, various slags, tailing are largely discharged and are accumulated, and cause extremely serious environment
Problem.
For devitrified glass majority currently on the market using natural minerals or pure chemicals as primary raw material, production cost is high,
Raw material reserves are relatively low, and cinder microcrystalline glass mainly coordinates a small amount of additive to be produced using various trade wastes,
It is of low cost, raw material rich reserves, while solving the environmental problem that waste residue is brought.
Increasingly increase severely with the discharge capacity of the solid waste such as slag, industrial residue.2009, China's industrial solid was discarded
Object is more than 2,000,000,000 tons, and within the nearest 7 years time, industrial solid castoff shows always burgeoning trend.It faces
The solid waste of substantial amounts, but only for small part for laying road, making cement, it is all outdoor heap that remaining is most of
It puts, while land occupation, a degree of environmental pollution also is caused to soil, river etc..These types are complicated, count
It is SiO to measure main component that is huge, being related to the numerous solid waste of industry mostly2, CaO, MgO etc., and these oxides
It is the primary raw material for producing devitrified glass glass, these solid waste is prepared into devitrified glass as primary raw material, are being become
While waste be changed into values, high, wear-resistant, the corrosion resistant new material of compact structure, intensity has also been obtained.Use industrial solid castoff
Prepare the approval that devitrified glass has also obtained domestic and international society.
Origin-state ash slag, is discharged by thermal power plant, and a degree of pollution is caused to ecological environment.Pass through composition detection
It was found that the main component of origin-state ash slag is：SiO2(20~70%), CaO (2~10%), Al2O3(20~40%) and Fe2O3
(2~8%).Therefore according to main component Proportionality design rational formula contained by various slags, in conjunction with the special of applicant's independent research
Sharp technology has developed " a method of using origin-state ash be main material production black micro-crystal glass plate ".Hope and is solving
Certainly when the larger slag waste of accumulating amount, also a little contribution is made to improve environmental problem.
Invention content
The present invention provides a kind of methods preparing black glass ceramic new material as primary raw material using origin-state ash slag.
The invention is realized in this way：
A method of black glass ceramic new material being prepared for primary raw material using origin-state ash, including：
Step 1: raw material selects：
Using origin-state ash slag as primary raw material, origin-state ash, magnesia unslacked, quartz sand, soda ash can be purchased on periphery, and change
Study point relatively stable, production cost is relatively low.
| Material name | Magnesia unslacked | Quartz sand | Origin-state ash | Soda ash |
| Weight ratio (%) | 6.2~11.2 | 4.2~13.5 | 67~85 | 2.9~12.5 |
Step 2: raw material mixes
It send after above-mentioned raw materials are weighed well in proportion and is mixed into batch mixer, and 2% water is added, mix 3~5 minutes
Afterwards, it send to All Electric Melting Furnace feeding chamber.
Step 3: the fusing of mixture
(1) it feeds：It is fed using automatic charging equipment, is controlled and fed by infrared ray liquid level indicator.
(2) fusing of mixture is carried out using All Electric Melting Furnace
All Electric Melting Furnace is divided into main melting tank, dog-hole, increased channel and several parts of material path, the fusing (fusion temperature of mixture
1450 DEG C~1550 DEG C), 8 hours or so (1400~1450 DEG C of the clarification and homogenization temperature) time of clarification and homogenization, in main molten
To change pond to carry out, clarification, the glass being homogenized enter material path through dog-hole, increased channel, and temperature is controlled at 1250 DEG C~1300 DEG C,
After material path cools down, calendaring molding (1050 DEG C~1150 DEG C of forming temperature) is carried out into calender.
Step 4: calendaring molding
Every production line uses two table glass calender (the using and the reserved) calendaring moldings, and plate thickness, width can be according to lifes
Production requires to be adjusted, and the communicated roller-way of glass tape of forming enters annealing kiln annealing.
Step 5: annealing
Glass tape enter annealing kiln temperature be 600~750 DEG C, at 600~700 DEG C keep the temperature 10~after twenty minutes, by 3 DEG C/
Divide~5 DEG C/minute of speed to be cooled to 520~600 DEG C, then 300 DEG C are cooled to by 7 DEG C/minute~12 DEG C/minute of speed, using
40 DEG C of kiln discharges are cooled within 40~60 minutes, subsequently into cold end cutting action.Cold end cutting action is wanted by sets requirement or client
The length asked cuts glass tape, forms semi-finished product (annealed sheet) after cutting, is sent to crystallization kiln crystallization through transition roller table.
Step 6: crystallization
The qualified annealed sheet of detection enters crystallization kiln, and 650 DEG C~710 DEG C were warming up to through 30~90 minutes, 650 DEG C~
710 DEG C of heat preservations coring in 30~90 minutes, 900 DEG C~950 DEG C had been warming up to through 30~90 minutes, were kept the temperature at 900 DEG C~950 DEG C
30~120 minutes crystallization were cooled to 40 DEG C of kiln discharges through 60~120 minutes, complete crystallization process.As hair plates (crystallization plate), send
Workshop is cut to mill to be finished.
Step 7: grinding and polishing
Detection qualified crystallization plate such as is polished through ZDML-16 full-automatic mills, is polished at the surfaces processing, and then storage is protected
It deposits.
The present invention can be used for producing black series devitrified glass, product compression strength using origin-state ash slag as primary raw material
250~300MPa, 60~70MPa of bending strength.
The present invention also has following features：
1. origin-state ash slag main chemical compositions are silica, alundum (Al2O3), calcium oxide, production crystallite glass can be used as
The primary raw material of glass, and can largely use.
2. origin-state ash slag can make devitrified glass that black be presented containing a small amount of transition metal ions, it is not necessarily to additional colorant,
Black glass ceramic can be produced, therefore raw material type is simple, facilitate production.
3. same cement, ceramics and glass industry compare (30% or so), which can efficiently utilize origin-state ash
Slag, utilization rate effectively solve the environmental hazard that waste residue is brought up to 80% or more.
Specific implementation mode
With reference to specific embodiment, the present invention is further illustrated.
Embodiment one
A method of black glass ceramic new material being prepared for primary raw material using origin-state ash, including：
1, by following raw material precises, it is sent into batch mixer mixing (incorporation time 4 minutes, add water 10kg).
| Material name | Magnesia unslacked | Quartz sand | Origin-state ash | Soda ash |
| Weight (kg) | 39.7 | 24.8 | 446.9 | 27.8 |
2, above-mentioned mixture is sent into All Electric Melting Furnace fusing, 1550 DEG C of fusion temperature, the glass melted is clarified and equal
After change, material path is entered by dog-hole, increased channel, temperature is down to 1250 DEG C, enters back into calendering work pool, rolls through calender
It shapes (1050 DEG C of forming temperature) and enters annealing kiln afterwards.
3, the glass board material annealing kiln after rolling is annealed, and is 700 DEG C into kiln temperature degree, after keeping the temperature 15 minutes at 650 DEG C,
550 DEG C are cooled to by 3 DEG C/minute of speed, then 300 DEG C are cooled to by 9 DEG C/minute of speed, 40 DEG C were cooled to using 60 minutes
Kiln discharge, subsequently into cold end cutting line.Cold end cutting line cuts glass tape by the length of sets requirement or customer requirement, cuts
Semi-finished product (annealed sheet) are generated afterwards, are sent to crystallization kiln crystallization through transition roller table.
4, the qualified annealed sheet of detection enters crystallization kiln, was warming up to 710 DEG C through 60 minutes, 60 minutes core is kept the temperature at 710 DEG C
Change, be warming up to 950 DEG C through 50 minutes, 60 minutes crystallization are kept the temperature at 950 DEG C, 40 DEG C of kiln discharges were cooled to through 120 minutes, completes
Crystallization process.As hair plates (crystallization plate), send to mill and cut workshop finishing.
5, plank color is black after polishing processing.
Embodiment two
A method of black glass ceramic new material being prepared for primary raw material using origin-state ash, including：
1, by following raw material precises, it is sent into batch mixer mixing (incorporation time 4 minutes, add water 8kg).
| Material name | Magnesia unslacked | Quartz sand | Origin-state ash | Soda ash |
| Weight (kg) | 54.0 | 69.5 | 371.7 | 55.2 |
2, above-mentioned mixture is sent into All Electric Melting Furnace fusing, 1450 DEG C of fusion temperature, the glass melted is clarified and equal
After change, material path is entered by dog-hole, increased channel, temperature is down to 1150 DEG C, enters back into calendering work pool, rolls through calender
It shapes (1000 DEG C of forming temperature) and enters annealing kiln afterwards.
3, the glass board material annealing kiln after rolling is annealed, and is 650 DEG C into kiln temperature degree, after keeping the temperature 15 minutes at 650 DEG C,
580 DEG C are cooled to by 3 DEG C/minute of speed, then 300 DEG C are cooled to by 9 DEG C/minute of speed, 40 DEG C were cooled to using 60 minutes
Kiln discharge, subsequently into cold end cutting line.Cold end cutting line cuts glass tape by the length of sets requirement or customer requirement, cuts
Semi-finished product (annealed sheet) are generated afterwards, are sent to crystallization kiln crystallization through transition roller table.
4, the qualified annealed sheet of detection enters crystallization kiln, was warming up to 650 DEG C through 60 minutes, 60 minutes core is kept the temperature at 650 DEG C
Change, be warming up to 900 DEG C through 50 minutes, 60 minutes crystallization are kept the temperature at 900 DEG C, 40 DEG C of kiln discharges were cooled to through 120 minutes, completes
Crystallization process.As hair plates (crystallization plate), send to mill and cut workshop finishing.
5, plank color is black after polishing processing.
Devitrified glass main performance index prepared by the embodiment of the present invention is as follows：
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that art technology
Personnel can be designed that a lot of other modification and implementations, these modifications and implementations will be fallen disclosed in the present application
Within scope and spirit.
Claims (3)
1. a kind of method preparing black glass ceramic new material using origin-state ash for primary raw material, it is characterised in that including as follows
Step：
Step 1: raw material selects：
Raw material is selected according to following weight ratio：
Step 2: raw material mixes
It send after above-mentioned raw materials are weighed well in proportion and is mixed into batch mixer, and the water for accounting for raw material gross weight 2% is added, mixing 3
~after five minutes, it send to All Electric Melting Furnace feeding chamber；
Step 3: the fusing of mixture
(1) it feeds：It is fed using automatic charging equipment, is controlled and fed by infrared ray liquid level indicator；
(2) fusing of mixture is carried out using All Electric Melting Furnace
All Electric Melting Furnace is divided into main melting tank, dog-hole, increased channel and several parts of material path, when the fusing of mixture, clarification and homogenization
Between 8 hours or so, carried out in main melting tank, clarification, the glass that has been homogenized enter material path, temperature control through dog-hole, increased channel
System is at 1250 DEG C~1300 DEG C, and after material path cools down, calendaring molding, forming temperature 1050 DEG C~1150 are carried out into calender
℃；
Step 4: calendaring molding
Every production line uses two table glass calender calendaring moldings, plate thickness, width to be adjusted according to production requirement, at
The communicated roller-way of glass tape of shape enters annealing kiln annealing；
Step 5: annealing
Glass tape enter annealing kiln temperature be 600~750 DEG C, at 600~700 DEG C keep the temperature 10~after twenty minutes, by 3 DEG C/minute~5
DEG C/minute speed be cooled to 520~600 DEG C, then 300 DEG C are cooled to by 7 DEG C/minute~12 DEG C/minute of speed, using 40~60
Minute is cooled to 40 DEG C of kiln discharges, subsequently into cold end cutting action；Cold end cutting action is by sets requirement or the length of customer requirement
Degree cuts glass tape, forms semi-finished product annealed sheet after cutting, is sent to crystallization kiln crystallization through transition roller table；
Step 6: crystallization
The qualified annealed sheet of detection enters crystallization kiln, 650 DEG C~710 DEG C is warming up to through 30~90 minutes, at 650 DEG C~710 DEG C
Coring in 30~90 minutes is kept the temperature, 900 DEG C~950 DEG C had been warming up to through 30~90 minutes, 30~120 are kept the temperature at 900 DEG C~950 DEG C
Minute crystallization was cooled to 40 DEG C of kiln discharges through 60~120 minutes, completes crystallization process, obtain crystallization plate.
2. the method for preparing black glass ceramic new material using origin-state ash for primary raw material according to claim 1, special
Sign is：
After step 6 obtains crystallization plate, crystallization plate is polished through ZDML-16 full-automatic mills, polished surface processing,
Then storage preserves.
3. the method according to claim 1 or claim 2 for preparing black glass ceramic new material using origin-state ash for primary raw material,
It is characterized in that：
In step 3, the fusion temperature of mixture is 1450 DEG C~1550 DEG C, the temperature of clarification and homogenization is 1400~1450 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110937815A (en) * | 2019-12-18 | 2020-03-31 | 中郡庄艺(泉州)新材料有限公司 | Preparation method of black glass ceramics by taking waste cement blocks as raw materials |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110937815A (en) * | 2019-12-18 | 2020-03-31 | 中郡庄艺(泉州)新材料有限公司 | Preparation method of black glass ceramics by taking waste cement blocks as raw materials |
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Application publication date: 20180814 |