CN105731808A - Method for preparing glass ceramics - Google Patents
Method for preparing glass ceramics Download PDFInfo
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- CN105731808A CN105731808A CN201610246107.3A CN201610246107A CN105731808A CN 105731808 A CN105731808 A CN 105731808A CN 201610246107 A CN201610246107 A CN 201610246107A CN 105731808 A CN105731808 A CN 105731808A
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- yellow phosphorus
- devitrified glass
- furnace slag
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002241 glass-ceramic Substances 0.000 title abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 80
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims description 67
- 239000002671 adjuvant Substances 0.000 claims description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 229910052681 coesite Inorganic materials 0.000 claims description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 229910052682 stishovite Inorganic materials 0.000 claims description 23
- 229910052905 tridymite Inorganic materials 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 10
- 229910001570 bauxite Inorganic materials 0.000 claims description 7
- 238000010587 phase diagram Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 3
- -1 sandstone Substances 0.000 claims description 3
- 210000003462 vein Anatomy 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011022 opal Substances 0.000 claims description 2
- 239000011044 quartzite Substances 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 abstract description 9
- 238000002425 crystallisation Methods 0.000 abstract description 8
- 238000000137 annealing Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052661 anorthite Inorganic materials 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 229910001720 Åkermanite Inorganic materials 0.000 description 6
- 229910017623 MgSi2 Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000006132 parent glass Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006063 cullet Substances 0.000 description 3
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 229910020472 SiO7 Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010786 composite waste Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 229910052638 hedenbergite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C03C10/0036—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
-
- 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
-
- 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
- C03C10/0009—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 silica as main constituent
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Organic 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)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing glass ceramics and belongs to the field of yellow phosphorus slag resource utilization. Yellow phosphorus slag is crushed, mixed and fused at a high temperature, and then micro-crystallization and annealing are conducted by controlling the cooling rate in the cooling process, so that the glass ceramics are prepared. The preparing process is simple and easy to implement, solid waste generated from industrial production serves as the raw material, produced glass ceramic panels can be widely applied to the industries including building materials, harmless treatment and recycling of slag are realized, and the environment can be protected.
Description
Technical field
The present invention relates to a kind of method that one-step method prepares devitrified glass, belong to industrial solid castoff processing technology field, i.e. waste residue resource field.
Background technology
At present, the method producing both at home and abroad yellow phosphorus is generally electric furnace process, adds in electric furnace by the mixture charge of rock phosphate in powder, Silicon stone and coke, passes into electric energy and converts heat energy to and melt and produce chemical reduction reaction, make phosphorus therein distil out, phosphorous furnace gas is condensed, separate after obtain finished product phosphorus.Yellow phosphorus furnace slag is that full-boiled process produces the industrial solid wastes produced in yellow phosphorus process, and its main component is CaO and SiO2, possibly together with a small amount of P2O5、Al2O3、Fe2O3, F etc..Often produce 1t yellow phosphorus and about discharge 8 ~ 10t slag.At present, both at home and abroad to the disposal options of yellow phosphorus furnace slag primarily as cement additive, roadbed material, calcium silicate fertilizer etc., the added value of these recycling modes is relatively low, eats the quantity of slag less.Devitrified glass, as high-grade construction decoration material, has higher added value, utilizes yellow phosphorus furnace slag to prepare devitrified glass, and what be possible not only to solution yellow phosphorus furnace slag stores up problem, also helps the comprehensive utilization of yellow phosphorus furnace slag.The yellow phosphorus furnace slag discharge capacity in Yunnan Province is very big, and the load that environment bears is also very big.Therefore, the process of yellow phosphorus furnace slag is extremely urgent with resource problem.At present, the comprehensive utilization of yellow phosphorus furnace slag becomes solid waste and processes and dispose and the study hotspot in resource field, be also phosphorous chemical industry sustainable development in the urgent need to.
Through the effort of domestic and international researcher for many years, the method that investigated the comprehensive utilization of some yellow phosphorus furnace slags, including yellow phosphorus furnace slag is used for producing cement additire, the construction material such as brickmaking, plate, calcium silicate fertilizer etc..But because of by technology and economic impact, adopting which kind of mode is the recycling approach of its best, does not come to a conclusion, causes the scale of yellow phosphorus furnace slag to utilize stagnation all the time.Devitrified glass, also known as glass ceramics, is make amorphous state parent glass be internally generated a large amount of uniform tiny crystals by control heat treating regime, day by day obtains extensive concern owing to it has the characteristic such as low water absorbable, higher mechanical strength.
It is make full use of Ca, Al, Si resource in solid waste yellow phosphorus furnace slag that the present invention utilizes big quantity of slag natural cooling yellow phosphorus furnace slag one-step method to prepare devitrified glass.Utilize yellow phosphorus furnace slag to produce devitrified glass, not only can consume yellow phosphorus furnace slag on a large scale to slow down the pressure of sulphur dioxide of phosphor chemical industry and to alleviate the yellow phosphorus furnace slag impact on ecological environment, and significantly high economical benefit can be produced.
Patent of invention CN101519277A discloses a kind of method that phosphorus slag produces calendaring type glass-ceramic decorative board.Wherein to adopt the phosphorus slag removing ferrum and coal ash impurity be 40% ~ 65%, quartz sand is 35% ~ 50%, soda is 8% ~ 14%, aluminium oxide is 3% ~ 8%, zinc oxide is 1% ~ 6%, magnesium oxide is 1% ~ 5%, brium carbonate is 1% ~ 6%, coloring agent is 0.5% ~ 4%, melten glass liquid in high temperature resistant tank furnace is down to 1200 DEG C ~ about 1260 DEG C be shaped, it is annealed processing between 900 DEG C ~ 960 DEG C, then cools down.Patent of invention CN103253867A discloses a kind of molten state yellow phosphorus furnace slag and prepares the Technology of devitrified glass.According to CaO-Al2O3-SiO2Ternary inorganic solution determines that yellow phosphorus furnace slag accounts for 51～78wt% of raw material total amount, will be enriched in SiO2And Al2O3Adjuvant add in molten state yellow phosphorus furnace slag and at high temperature to carry out clarification moulding by casting, at 600 DEG C～650 DEG C, be incubated 1h～2h after annealing, and carry out follow-up coring, crystallization process, obtain devitrified glass.Patent of invention CN1868946A discloses a kind of waste residue microcrystal glass and preparation method thereof.The raw material of preparing of this waste residue microcrystal glass is mainly the composite waste of yellow phosphorus furnace slag, Ta Nb tailings and cullet, and requiring to add adjuvant according to the chemical composition of this waste residue microcrystal glass, percentage by weight shared by described yellow phosphorus furnace slag, Ta Nb tailings, cullet and each raw material of adjuvant is: yellow phosphorus furnace slag 28 ~ 55%, Ta Nb tailings 10 ~ 30%, cullet 10 ~ 18%, adjuvant 3 ~ 45%.Patent of invention CN101037298A discloses a kind of method comprehensively utilizing yellow phosphorus slag and End gas production devitrified glass.This patent of invention utilizes the nozzle of melting furnace furnace roof ordered arrangement by dried for water washing cleaning yellow phosphoric tail gas and oxygen mix after-combustion, maintains in-furnace temperature 1450 DEG C to reach effectively to utilize the yellow phosphoric tail gas exothermic purpose of burning.And directly add silicon, aluminum, sodium raw materials to yellow phosphorus molten slag in melting furnace, obtain devitrified glass finished product then through coring, Crystallizing treatment.
At present, waste residue is utilized to prepare in the resource mode of devitrified glass disclosed in being able to, the waste residue amount mostly adopted be 40 ~ 70% and coring, crystallization two-step method prepare the mode of devitrified glass, this mode exists that to eat the quantity of slag less, the problems such as energy consumption is bigger, and depressed due to yellow phosphorus industry in recent years, its economic benefit weakens increasingly.The present invention is under the premise of the big quantity of slag, realizes one-step method prepare devitrified glass by controlling rate of temperature fall and temperature retention time, and technique is easy, and energy consumption is greatly reduced, good economy performance.
Summary of the invention
It is an object of the invention to provide a kind of method preparing devitrified glass, yellow phosphorus furnace slag is broken, batch mixing so that it is be melted into liquid at high operating temperatures, prepare devitrified glass then through process one-step method such as the controlled micro crystallization process in temperature-fall period, annealing.Specifically include following steps:
(1) yellow phosphorus furnace slag obtains yellow phosphorus furnace slag powder after broken, grinding, screening；
(2) according to CaO-Al under different temperatures2O3-SiO2Liquidus temperature range in ternary phase diagrams, it is determined that yellow phosphorus furnace slag accounts for 61 ~ 83wt% of raw material total amount, rich in SiO2Adjuvant accounts for 8 ~ 16wt% of raw material total amount, rich in Al2O3Adjuvant accounts for 8 ~ 23wt% of raw material total amount, the adjuvant of yellow phosphorus furnace slag powder and 80-200 order is mixed and is placed at 1350 ~ 1450 DEG C and is incubated 90 ~ 120min makes it all melt, then after cooling to 850 ~ 950 DEG C of insulation 120 ~ 180min with the rate of temperature fall of 1 ~ 5 DEG C/min, cool to room temperature with the rate of temperature fall of 8 ~ 15 DEG C/min again, namely obtain devitrified glass.
Described rich in SiO2Adjuvant is the one in vein quartz, quartz sand, quartzite, sandstone, Silicon stone, opal, kieselguhr, SiO in adjuvant2Content more than 70%.
Described rich in Al2O3Adjuvant is bauxite, Al in adjuvant2O3Content is be more than or equal to 90%.
Principles of the invention: utilize CaO-Al2O3-SiO2Ternary system phasor, redesigns the devitrified glass of the big quantity of slag, improves the utilization rate of yellow phosphorus furnace slag；And utilize point facies principle in glass, by controlling rate of temperature fall in temperature-fall period, solid-liquid phase separates to make inside glass occur, produces small grains, and insulation a period of time makes the grain growth of inside glass become crystal.
Beneficial effects of the present invention:
(1) method that yellow phosphorus furnace slag of the present invention prepares devitrified glass, simple for process, and the process such as, controlled micro crystallization process melted through the condition of high temperature, annealing prepares the devitrified glass of excellent performance；
(2) present invention can prepare akermanite and the devitrified glass of cacoclasite crystalline phase, forms the economic chain of phosphorus slag resource recycling, it is achieved phosphorus slag is innoxious, higher value application；
(3) controlled micro crystallization carried out in temperature-fall period of the present invention processes and can be greatly saved the energy, simplifies heat treatment step, improves economic worth.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the devitrified glass that the embodiment of the present invention 1 prepares；
Fig. 2 is the SEM figure of the devitrified glass that the embodiment of the present invention 1 prepares；
Fig. 3 is the XRD figure of the devitrified glass that the embodiment of the present invention 2 prepares；
Fig. 4 is the SEM figure of the devitrified glass that the embodiment of the present invention 2 prepares；
Fig. 5 is the XRD figure of the devitrified glass that the embodiment of the present invention 3 prepares；
Fig. 6 is the SEM figure of the devitrified glass that the embodiment of the present invention 3 prepares；
Fig. 7 is the XRD figure of the devitrified glass that the embodiment of the present invention 4 prepares；
Fig. 8 is the SEM figure of the devitrified glass that the embodiment of the present invention 4 prepares；
Fig. 9 is the XRD figure of the devitrified glass that contrast test prepares；
Figure 10 is the SEM figure of the devitrified glass that contrast test prepares.
Detailed description of the invention
The present invention is made full and clear further below in conjunction with embodiment, but scope is not limited to described content.
Embodiment 1:Yellow phosphorus furnace slag described in the present embodiment is that full-boiled process produces solid waste produced by yellow phosphorus technique, and the composition of its raw material is as shown in table 1:
Table 1: yellow phosphorus furnace slag raw material key component
；
(1) yellow phosphorus furnace slag is after broken, grinding, crossing 80 mesh sieves screenings, obtains yellow phosphorus furnace slag powder；
(2) according to CaO-Al under different temperatures2O3-SiO2Liquidus temperature range in ternary phase diagrams, it is determined that yellow phosphorus furnace slag accounts for the 82.35wt% of raw material total amount, rich in SiO2Adjuvant accounts for the 8.43wt%(quartz sand of raw material total amount, SiO in adjuvant2Be 95%), rich in Al2O3Adjuvant accounts for the 9.22wt%(bauxite of raw material total amount, Al in adjuvant2O3Content is 92%)；The yellow phosphorus furnace slag powder obtain step (1) and the adjuvant of 100 ~ 200 orders are put in alumina crucible and are placed in high-temperature ceramic fibre Muffle furnace, 120min it is incubated at 1400 DEG C, then after cooling to 900 DEG C of insulation 130min with the rate of temperature fall of 5 DEG C/min, cool to room temperature with the rate of temperature fall of 8 DEG C/min again, can obtain devitrified glass (see Fig. 1,2).
Through XRD analysis it can be seen that the principal crystalline phase in devitrified glass is Ca2MgSi2O7(akermanite) and Ca2Al2SiO7(cacoclasite), the average crystal grain probably calculated in devitrified glass by Scherrer formula is sized to 16.2nm, and degree of crystallinity is 61.30%, and as can be seen from Figure 2 the distribution of the crystal grain in devitrified glass comparatively disperses, and crystal grain is less and in irregular shape.
Embodiment 2:In the present embodiment, yellow phosphorus furnace slag is that full-boiled process produces solid waste produced by yellow phosphorus technique, and the composition of its raw material is as shown in table 2:
Table 2: yellow phosphorus furnace slag raw material key component
；
(1) yellow phosphorus furnace slag is after broken, grinding, crossing 80 mesh sieves screenings, obtains yellow phosphorus furnace slag powder；
(2) according to CaO-Al under different temperatures2O3-SiO2Liquidus temperature range in ternary phase diagrams, it is determined that yellow phosphorus furnace slag accounts for the 81.45wt% of raw material total amount, rich in SiO2Adjuvant accounts for the 10.32wt%(Silicon stone of raw material total amount, SiO in adjuvant2Be 98%), rich in Al2O3Adjuvant accounts for the 8.23wt%(bauxite of raw material total amount, Al in adjuvant2O3Content is 91%)；The yellow phosphorus furnace slag powder obtain step (1) and the adjuvant of 80 ~ 100 orders are put in alumina crucible and are placed in high-temperature ceramic fibre Muffle furnace, 120min it is incubated at 1350 DEG C, then after cooling to 870 DEG C of insulation 170min with the rate of temperature fall of 1 DEG C/min, cool to room temperature with the rate of temperature fall of 10 DEG C/min again, can obtain devitrified glass (see Fig. 3,4).
Through XRD analysis it can be seen that the principal crystalline phase in devitrified glass is Ca2MgSi2O7(akermanite) and Ca2Al2SiO7(cacoclasite), the average crystal grain probably calculated in devitrified glass by Scherrer formula is sized to 23.1nm, and degree of crystallinity is 66.05%, and as can be seen from Figure 4 the different crystalline phases in devitrified glass present difformity, big compared with in example 1 of grain size.
Embodiment 3:In the present embodiment, yellow phosphorus furnace slag is that full-boiled process produces solid waste produced by yellow phosphorus technique, and the composition of its raw material 3 is as shown in table 3:
Table 3: yellow phosphorus furnace slag raw material key component
；
(1) yellow phosphorus furnace slag is after broken, grinding, crossing 80 mesh sieves screenings, obtains yellow phosphorus furnace slag powder；
(2) according to CaO-Al under different temperatures2O3-SiO2Liquidus temperature range in ternary phase diagrams, it is determined that yellow phosphorus furnace slag accounts for the 80.45wt% of raw material total amount, rich in SiO2Adjuvant accounts for the 11.32wt%(vein quartz of raw material total amount, SiO in adjuvant2Be 99%), rich in Al2O3Adjuvant accounts for the 8.23wt%(bauxite of raw material total amount, Al in adjuvant2O3Content is 95%)；The yellow phosphorus furnace slag powder obtain step (1) and the adjuvant of 100 ~ 150 orders are put in alumina crucible and are placed in high-temperature ceramic fibre Muffle furnace, 90min it is incubated at 1450 DEG C, then after cooling to 950 DEG C of insulation 120min with the rate of temperature fall of 3 DEG C/min, cool to room temperature with the rate of temperature fall of 15 DEG C/min again, can obtain devitrified glass (see Fig. 5,6).
Through XRD analysis it can be seen that the principal crystalline phase in devitrified glass is Ca2MgSi2O7(akermanite) and CaAl2Si2O8(anorthite), the average crystal grain probably calculated in devitrified glass by Scherrer formula is sized to 33.3nm, and degree of crystallinity is 77.41%, and as can be seen from Figure 6 the grain size in devitrified glass differs, but it is distributed comparatively dense, also presents irregular shape.
Embodiment 4:In the present embodiment, yellow phosphorus furnace slag is that full-boiled process produces solid waste produced by yellow phosphorus technique, and the composition of its raw material is as shown in table 4:
Table 4: yellow phosphorus furnace slag raw material key component
；
(1) yellow phosphorus furnace slag is after broken, grinding, crossing 80 mesh sieves screenings, obtains yellow phosphorus furnace slag powder；
(2) according to CaO-Al under different temperatures2O3-SiO2Liquidus temperature range in ternary phase diagrams, it is determined that yellow phosphorus furnace slag accounts for the 63.21wt% of raw material total amount, rich in SiO2Adjuvant accounts for the 31.05wt%(kieselguhr of raw material total amount, SiO in adjuvant2Be 75%), rich in Al2O3Adjuvant accounts for the 5.74wt%(bauxite of raw material total amount, Al in adjuvant2O3Content is 96%)；The yellow phosphorus furnace slag powder obtain step (1) and the adjuvant of 120 ~ 180 orders are put in alumina crucible and are placed in high-temperature ceramic fibre Muffle furnace, 100min it is incubated at 1380 DEG C, then after cooling to 930 DEG C of insulation 140min with the rate of temperature fall of 2 DEG C/min, cool to room temperature with the rate of temperature fall of 10 DEG C/min again, can obtain devitrified glass (see Fig. 7,8).
Through XRD analysis it can be seen that the principal crystalline phase in devitrified glass is Ca2MgSi2O7(akermanite) and CaAl2Si2O8(anorthite), the average crystal grain probably calculated in devitrified glass by Scherrer formula is sized to 19.9nm, and degree of crystallinity is 82.41%, as can be seen from Figure 8 the distribution of the crystal grain in devitrified glass densification, and based on spherical and needle-like, degree of crystallinity is higher.
Embodiment 5:In the present embodiment, yellow phosphorus furnace slag is that full-boiled process produces solid waste produced by yellow phosphorus technique, and the composition of its raw material is as shown in table 5:
Table 5: yellow phosphorus furnace slag raw material key component
；
(1) yellow phosphorus furnace slag is after broken, grinding, crossing 80 mesh sieves screenings, obtains yellow phosphorus furnace slag powder；
(2) according to CaO-Al under different temperatures2O3-SiO2Liquidus temperature range in ternary phase diagrams, it is determined that yellow phosphorus furnace slag accounts for the 75.26wt% of raw material total amount, rich in SiO2Adjuvant accounts for the 21.35wt%(sandstone of raw material total amount, SiO in adjuvant2Be 95%), rich in Al2O3Adjuvant accounts for the 3.39wt%(bauxite of raw material total amount, Al in adjuvant2O3Content is 95%)；The yellow phosphorus furnace slag powder obtain step (1) and the adjuvant of 150 ~ 180 orders are put in alumina crucible and are placed in high-temperature ceramic fibre Muffle furnace, 90min it is incubated at 1400 DEG C, then after cooling to 920 DEG C of insulation 120min with the rate of temperature fall of 4 DEG C/min, cool to room temperature with the rate of temperature fall of 12 DEG C/min again, devitrified glass can be obtained.
Through XRD analysis it can be seen that the principal crystalline phase in devitrified glass is Ca2MgSi2O7(akermanite) and CaAl2Si2O8(anorthite), the average crystal grain probably calculated in devitrified glass by Scherrer formula is sized to 24.5nm, and degree of crystallinity is 78.41%, and the obtained die outline in devitrified glass is needle-like, threadiness distribution, and compact structure, degree of crystallization is higher.
Attached:Contrast with a kind of patent Technology of devitrified glass (molten state yellow phosphorus furnace slag prepare) method:
The composition of raw material is as shown in table 6:
Table 6: yellow phosphorus furnace slag raw material key component
According to CaO-Al2O3-SiO2Ternary inorganic solution determines the composition of raw materials preparing devitrified glass, and yellow phosphorus furnace slag accounts for the 75.60wt% of raw material total amount, rich in SiO2Adjuvant accounts for the 19.39wt%(quartz sand of raw material total amount, SiO in adjuvant2Be 95%), Al2O3It is commercially available chemical pure aluminium oxide that adjuvant accounts for the 5.01wt%(adjuvant aluminium oxide of raw material total amount)；Adjuvant is added in yellow phosphorus furnace slag, at 1350 DEG C, be incubated 120min melt parent glass raw material, then parent glass liquation is poured into rapidly die for molding, 600 DEG C of bodies of heater are incubated 2h after annealing；By parent glass with the coring heating rate of 5 DEG C/min rise to 790 DEG C insulation 2h, then with the crystallization heating rate of 3 DEG C/min rise to 1080 DEG C insulation 1.5h after obtain devitrified glass with stove natural cooling.
Through the known (see figure 9) of XRD analysis, the principal crystalline phase in devitrified glass is wollastonite (CaSiO3) and hedenbergite ((Ca, Fe) SiO3), the average crystal grain probably calculated in devitrified glass by Scherrer formula is sized to 50.6nm, and degree of crystallinity is 41.87%, it is observed that substantial amounts of spherical particle overall distribution are comparatively uniform from Figure 10, the growth promoter of crystal is good.
Claims (3)
1. the method preparing devitrified glass, it is characterised in that: according to CaO-Al under different temperatures2O3-SiO2Liquidus temperature range in ternary phase diagrams, it is determined that yellow phosphorus furnace slag accounts for 61 ~ 83wt% of raw material total amount, rich in SiO2Adjuvant accounts for 8 ~ 16wt% of raw material total amount, rich in Al2O3Adjuvant accounts for 8 ~ 23wt% of raw material total amount, by grind screening after yellow phosphorus furnace slag powder and 80 ~ 200 purposes rich in SiO2Adjuvant, rich in Al2O3Adjuvant mixing is placed at 1350 ~ 1450 DEG C and is incubated 90 ~ 120min makes it all melt, and after then cooling to 850 ~ 950 DEG C of insulation 120 ~ 180min with the rate of temperature fall of 1 ~ 5 DEG C/min, then cools to room temperature with the rate of temperature fall of 8 ~ 15 DEG C/min, namely obtains devitrified glass.
2. the method preparing devitrified glass according to claim 1, it is characterised in that: rich in SiO2Adjuvant is the one in vein quartz, quartz sand, quartzite, sandstone, Silicon stone, opal, kieselguhr, SiO in adjuvant2Content more than 70%.
3. the method preparing devitrified glass according to claim 1, it is characterised in that: rich in Al2O3Adjuvant is bauxite, Al in adjuvant2O3Content is be more than or equal to 90%.
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| CN106365439A (en) * | 2016-08-26 | 2017-02-01 | 云南碧霄环保科技有限公司 | Method for harmless and resourceful treatment of metallurgical hazardous waste |
| CN106565096A (en) * | 2016-10-31 | 2017-04-19 | 昆明理工大学 | Method for preparing glass-ceramic by using carbide slag |
| US20200017399A1 (en) * | 2018-07-16 | 2020-01-16 | Corning Incorporated | Glass-ceramic articles with increased resistance to fracture and methods for making the same |
| CN114477772A (en) * | 2022-01-30 | 2022-05-13 | 山东国瓷功能材料股份有限公司 | High strength, high permeability glass-ceramic structures, methods of making same, and resulting products |
| US11613491B2 (en) | 2018-07-16 | 2023-03-28 | Corning Incorporated | Methods of ceramming glass articles having improved warp |
| US11649187B2 (en) | 2018-07-16 | 2023-05-16 | Corning Incorporated | Glass ceramic articles having improved properties and methods for making the same |
| US11834363B2 (en) | 2018-07-16 | 2023-12-05 | Corning Incorporated | Methods for ceramming glass with nucleation and growth density and viscosity changes |
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| CN106565096A (en) * | 2016-10-31 | 2017-04-19 | 昆明理工大学 | Method for preparing glass-ceramic by using carbide slag |
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| US20200017399A1 (en) * | 2018-07-16 | 2020-01-16 | Corning Incorporated | Glass-ceramic articles with increased resistance to fracture and methods for making the same |
| US11613491B2 (en) | 2018-07-16 | 2023-03-28 | Corning Incorporated | Methods of ceramming glass articles having improved warp |
| US11649187B2 (en) | 2018-07-16 | 2023-05-16 | Corning Incorporated | Glass ceramic articles having improved properties and methods for making the same |
| US11834363B2 (en) | 2018-07-16 | 2023-12-05 | Corning Incorporated | Methods for ceramming glass with nucleation and growth density and viscosity changes |
| CN114477772A (en) * | 2022-01-30 | 2022-05-13 | 山东国瓷功能材料股份有限公司 | High strength, high permeability glass-ceramic structures, methods of making same, and resulting products |
| CN114477772B (en) * | 2022-01-30 | 2023-07-25 | 山东国瓷功能材料股份有限公司 | High-strength high-permeability glass ceramic structure, preparation method thereof and obtained product |
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