CN106565096A - Method for preparing glass-ceramic by using carbide slag - Google Patents
Method for preparing glass-ceramic by using carbide slag Download PDFInfo
- Publication number
- CN106565096A CN106565096A CN201610926640.4A CN201610926640A CN106565096A CN 106565096 A CN106565096 A CN 106565096A CN 201610926640 A CN201610926640 A CN 201610926640A CN 106565096 A CN106565096 A CN 106565096A
- Authority
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- China
- Prior art keywords
- rich
- auxiliary material
- carbide slag
- glass
- raw material
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002893 slag Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 62
- 239000002994 raw material Substances 0.000 claims abstract description 51
- 238000002844 melting Methods 0.000 claims abstract 2
- 230000008018 melting Effects 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 45
- 239000011521 glass Substances 0.000 claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 229910052681 coesite Inorganic materials 0.000 claims description 34
- 229910052906 cristobalite Inorganic materials 0.000 claims description 34
- 229910052682 stishovite Inorganic materials 0.000 claims description 34
- 229910052905 tridymite Inorganic materials 0.000 claims description 34
- 239000000292 calcium oxide Substances 0.000 claims description 31
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 31
- 229910052593 corundum Inorganic materials 0.000 claims description 29
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 8
- 239000006004 Quartz sand Substances 0.000 claims description 7
- 229910001570 bauxite Inorganic materials 0.000 claims description 7
- 235000017550 sodium carbonate Nutrition 0.000 claims description 7
- 239000004575 stone Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 2
- 238000007507 annealing of glass Methods 0.000 abstract 1
- 239000006121 base glass Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 238000007088 Archimedes method Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 239000010881 fly ash Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000011449 brick Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011494 foam glass Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006132 parent glass Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229910014813 CaC2 Inorganic materials 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011469 building brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
Abstract
The invention discloses a method for preparing glass-ceramic by using carbide slag, and belongs to the field of resource utilization of carbide slag. The method comprises: pre-treating carbide slag at a high temperature, mixing with an auxiliary material, melting at a high temperature, and carrying out base glass annealing, microcrystalline treatment and other processes to prepare the high added value glass-ceramic. According to the present invention, the prepared glass-ceramic has characteristics of high utilization value, simple process and the like, the raw material is the solid waste produced in the industrial production process, the produced glass-ceramic can be widely used in the building materials and other industries, and the harmless and resource utilization of the carbide slag is achieved.
Description
Technical field
The present invention relates to a kind of method that utilization carbide slag prepares devitrified glass, belongs to industrial solid wastes disposal technology neck
Domain, i.e. waste residue resource field.
Background technology
Carbide slag is the hydrolysising by-product produced during calcium carbide hydrolysis production acetylene, and key reaction formula sees below formula；
CaC2+2H2O→C2H2+Ca(OH)2
Main component is calcium hydroxide and calcium carbonate, and the generation of component calcium carbonate is due to the dioxy in calcium hydroxide absorption air
Change what carbon was caused.In addition there is a small amount of SiO2、Al2O3、Fe2O3Etc. component, belong to high calcium alkaline residue.At present, it is right both at home and abroad
The process disposal options of carbide slag mainly have stores up and comprehensively utilizes two kinds, and substantial amounts of soil do not only take up in is stored up for a large amount of carbide slags
Ground resource, increases entreprise cost, equally causes the pollution of soil, water body, air, becomes restriction industry development and destruction is ecological
The key factor of environment；Comprehensive utilization is largely focused on replacement calcareous material to produce cement, building brick, insulation material
Deng.These disposal options have that to eat the quantity of slag big, the features such as environmentally friendly, but the product produced by means of which have it is attached
Value added low shortcoming.Devitrified glass is a kind of a kind of top-grade building decoration material prepared by control composition and heat treating regime
Material, can be widely used for the industries such as building materials.The devitrified glass of different system has larger restriction, such as CaO-Al to its component2O3-
SiO2System glass ceramics have higher to the compositional range of the calcium containing compound in system, aluminum contained compound and silicon-containing compound
Require.Calcium hydroxide and calcium carbonate in carbide slag can be changed into after pretreatment the calcium oxide of high-load, be to prepare CaO-Al2O3-
SiO2The main composition of system glass ceramics.
It is to make full use of high Ca resources in solid waste carbide slag that the present invention prepares devitrified glass using carbide slag, and to electricity
A small amount of SiO in rock ballast2、Al2O3、Fe2O3Abundant recycling is carried out etc. component.CaO-Al is prepared using carbide slag2O3-
SiO2System glass ceramics not only can significantly slow down carbide slag and store up the impact for taking a large amount of soils, and the crystallite produced
Glass has higher economic benefit.
Patent of invention CN102795772A is disclosed one kind and is prepared using kaolin type gangue or flyash and carbide slag
The method of devitrified glass.The method for preparing devitrified glass is first gangue, flyash and carbide slag to be carried out into carbon elimination, iron, stone
The pretreatment of electrode ink chip, is 10 ~ 55% according still further to gangue boiler ash sediment or flyash, and carbide slag is 8 ~ 24%, silica
For 20 ~ 55%, the mass percent such as sodium oxide molybdena 5 ~ 12% carries out dispensing, the particle that a part do not melt is retained in melting process and is made
Devitrified glass product is thermally treated resulting in for the nucleus of subsequent heat treatment, then process.Application for a patent for invention CN103833276A is disclosed
A kind of environment-friendly light carbide slag aerated bricks and preparation method thereof.Wherein adopt carbide slag 24 ~ 26%, flyash 9 ~ 11%, glass
Fiber 2 ~ 4% etc., construction refuse regenerated powder（Including construction refuse regenerated concrete powder and/or construction refuse regenerated brick powder）11~
14% calcines 3 ~ 4h at 770 ~ 850 DEG C, adds 1 ~ 3h of precuring at diatomite 15 ~ 19%, cement 4 ~ 7% etc. are blended in 35 ~ 44 DEG C
After obtain base of laying bricks, then put it into 13 ~ 15h of maintenance in reactor, that is, obtain lightweight carbide slag aerated bricks.Patent of invention
CN103193390A discloses the preparation method of carbide slag foam glass thermal insulation material.The patent of invention is with 70% ~ 90% glass
Powder, 10% ~ 30% carbide slag add appropriate auxiliary additive with 5 ~ 10 DEG C/min's for raw material and with sodium carbonate as foaming agent
Ramp is to 600 DEG C and is incubated 30min；So that the ramp of 10 ~ 15 DEG C/min is to 800 ~ 950 DEG C and is incubated 20 ~ 40min；
550 ~ 650 DEG C are cooled to the rate of temperature fall of 15 ~ 20 DEG C/min；It is annealed to room temperature with the rate of temperature fall of 1 ~ 2 DEG C/min again to obtain
Carbide slag foam glass thermal insulation material.Application for a patent for invention CN103738997A is disclosed with carbide slag as waste nano-sized carbon
The method of sour calcium.The pretreatment such as separation of solid and liquid, impurity elimination, decolouring is carried out to carbide slag first, by controlling its pH value 12 or so
It is dissolved in leaching in ammonium chloride solution to obtain being passed through carbon dioxide gas in calcium chloride solution, then the solution after filtering to leaching
Body carries out carburizing reagent, finally gives spherical superfine nano calcium carbonate.Due to the alkaline nature of carbide slag, many researchers
Then come treatment of acidic wastewater and sour gas as raw material, such as patent of invention CN104192970A discloses a kind of process acid
Property waste water carbide slag slow-release material and preparation method thereof, application for a patent for invention CN104984658A discloses a kind of carbide slag and takes off
Sulphur system etc..It is this to adopt " treatment of wastes with processes of wastes against one another " thinking, by the method for the special nature treatment of acidic wastewater or gas of carbide slag
Also extensively utilized.
At present, in being able to disclosed carbide slag recycling mode, the added value of product for obtaining is relatively low；And it is special in invention
A kind of method that utilization kaolin type gangue or flyash and carbide slag disclosed in sharp CN102795772A prepare devitrified glass
The utilization rate of middle carbide slag is only 8 ~ 24%, eats that the quantity of slag is less not to be fully used；And pass through carbide slag and extract nano-calcium carbonate
During the chemicals such as calcium, need to wherein a small amount of SiO2、Al2O3、Fe2O3Impurity elimination is carried out etc. component so that technique is complex.
The present invention is to adopt to carry out pre-treatment to carbide slag so that the consumption of carbide slag is significantly improved, the CaO-Al for preparing2O3-
SiO2The added value of microcrystalline glass in series is higher, better economy.
The content of the invention
It is an object of the invention to provide a kind of method that utilization carbide slag prepares devitrified glass, first by carbide slag in height
Pre-treatment is carried out under temperature, the higher oxidation calcium product of content is obtained, and by with auxiliary material SiO2、Al2O3And Na2CO3Mixed,
Melt at high temperature and obtain parent glass for liquid, then CaO-Al is prepared through glass-ceramic process2O3-SiO2It is crystallite glass
Glass.Specifically include following steps：
（1）By carbide slag in high temperature Muffle furnace, with the heating rate of 5 ~ 7 DEG C/min 700 ~ 800 DEG C are raised to, then with 1 ~ 3 DEG C/
The ramp of min is to 1000 ~ 1100 DEG C and is incubated 90 ~ 150min, then cools to room temperature with the furnace and obtain the raw material rich in CaO,
Wherein CaO content >=80wt%；
（2）By step（1）The raw material rich in CaO that obtains and rich in SiO2Auxiliary material, rich in Al2O3Auxiliary material and be rich in
Na2CO3Auxiliary material mix 90 ~ 120min in mixer, the raw material rich in CaO accounts for 40 ~ 55wt% of raw material total amount, rich in SiO2
Auxiliary material account for 34 ~ 55wt% of raw material total amount, rich in Al2O3Auxiliary material account for 2 ~ 5wt% of raw material total amount, rich in Na2CO3Auxiliary material
3 ~ 7wt% of raw material total amount is accounted for, being subsequently placed in alumina crucible makes it melt in high temperature Muffle furnace, and at 1350-1450 DEG C
Carry out being made annealing treatment at thermal state forming is placed in 600-650 DEG C after lower insulation 90-150min.Process through glass-ceramic process again
To devitrified glass.
It is described rich in SiO2Auxiliary material be quartz sand etc., wherein SiO2Content is more than or equal to 75wt%.
It is described rich in Al2O3Auxiliary material be bauxite, wherein Al2O3Content is more than or equal to 80wt%.
It is described rich in Na2CO3Auxiliary material be soda, crystal soda, soda ash, washing soda in one kind, wherein Na2CO3Content is more than
Equal to 70wt%.
Step（2）Described in glass-ceramic process processing method be conventional method, for example can refer to described in documents below
Method is processed：Liu Hongpan etc., TiO2Impact [J] to natural cooling yellow phosphorus furnace slag ceramics behavior. it is artificial brilliant
Body journal, 2014,06:1561-1567..
The principle of the present invention：Easily it is decomposed into the spy of calcium oxide at high temperature using calcium hydroxide in carbide slag and calcium carbonate
Property, without the need for carrying out dedoping step to it, make full use of the SiO in carbide slag2、Al2O3、Fe2O3Etc. component.SiO2And Al2O3As
CaO-Al2O3-SiO2The constitutive material of microcrystalline glass in series, Fe2O3As CaO-Al2O3-SiO2The Nucleating Agent of microcrystalline glass in series is promoting
Enter crystallization.
Beneficial effects of the present invention：
（1）The method that carbide slag of the present invention prepares devitrified glass, it is simple for process, after pretreatment, mix with auxiliary material
Melted at high operating temperatures, controlled micro crystallization process, the process such as annealing prepare the devitrified glass of excellent performance；
（2）The present invention can prepare the devitrified glass of excellent performance, form the economic chain of carbide slag resource recycling, realize carbide slag
Innoxious, higher value application；
（3）It is of the present invention to prepare during devitrified glass, without the need for carrying out to raw material except miscellaneous operation, and make full use of in carbide slag
Impurity composition, improve economic worth.
Description of the drawings
Fig. 1 prepares devitrified glass process chart for carbide slag of the present invention.
Specific embodiment
The present invention is described in further detail with reference to embodiment, but the scope of the present invention is not limited in described
Hold.
Embodiment 1
（1）By carbide slag in high temperature Muffle furnace, 800 DEG C are raised to the heating rate of 5 DEG C/min, then with the speed of 3 DEG C/min
Rate is warmed up to 1000 DEG C and is incubated 90min, then cools to room temperature with the furnace and obtain the raw material rich in CaO, and wherein CaO content is
90.02wt%；
（2）By step（1）The raw material rich in CaO that obtains and rich in SiO2Auxiliary material, rich in Al2O3Auxiliary material and be rich in
Na2CO3Auxiliary material mix 90min in mixer, the raw material rich in CaO accounts for the 40wt% of raw material total amount, rich in SiO2Auxiliary material
Account for the 54.22wt% of raw material total amount（Quartz sand, wherein SiO2Content is 75wt%）, rich in Al2O3Auxiliary material account for raw material total amount
2.53wt%（Bauxite, wherein Al2O3Content is 80wt%）, rich in Na2CO3Auxiliary material account for the 3.25wt% of raw material total amount（Soda,
Wherein Na2CO3Content is 70wt%）.Being subsequently placed in alumina crucible makes it melt in high temperature Muffle furnace, and at 1400 DEG C
Carry out being made annealing treatment at thermal state forming is placed in 650 DEG C after insulation 120min.Obtain through a series of process of glass-ceramic processes again
Devitrified glass.
Controlled micro crystallization processing procedure：Parent glass is risen to into 780 DEG C of insulation 2h with the heating rate of 2 ~ 5 DEG C/min, then with 1 ~ 2
DEG C/heating rate of min rises to be cooled down after 1080 DEG C of insulation 1.5h and be obtained devitrified glass.
Using the bulk density of Archimedes method determination sample, foundation《Expectation of Glass-Ceramics Used as Decorated Materials JC/T872-
2000》, determine the water absorption rate of sample.As a result show, the bulk density of this devitrified glass is 2.2206 cm3/ g, water absorption rate is
0.023%。
Embodiment 2
（1）By carbide slag in high temperature Muffle furnace, 700 DEG C are raised to the heating rate of 7 DEG C/min, then with the speed of 2 DEG C/min
Rate is warmed up to 1050 DEG C and is incubated 120min, then cools to room temperature with the furnace and obtain the raw material rich in CaO, and wherein CaO content is
88.03wt%；
（2）By step（1）The raw material rich in CaO that obtains and rich in SiO2Auxiliary material, rich in Al2O3Auxiliary material and be rich in
Na2CO3Auxiliary material mix after 100min in mixer, being placed in alumina crucible makes it melt in high temperature Muffle furnace.It is rich in
The raw material of CaO accounts for the 48wt% of raw material total amount, rich in SiO2Auxiliary material account for the 44.07wt% of raw material total amount（Quartz sand, wherein SiO2
Content is 80wt%）, rich in Al2O3Auxiliary material account for the 3.72wt% of raw material total amount（Bauxite, wherein Al2O3Content is 85wt%）,
Rich in Na2CO3Auxiliary material account for the 4.21wt% of raw material total amount（Crystal soda, wherein Na2CO3Content is 72wt%）.It is incubated at 1350 DEG C
Carry out being made annealing treatment at thermal state forming is placed in 640 DEG C after 150min.Obtain crystallite through a series of process of glass-ceramic processes again
Glass.
Using the bulk density of Archimedes method determination sample, foundation《Expectation of Glass-Ceramics Used as Decorated Materials JC/T872-
2000》, determine the water absorption rate of sample.As a result show, the bulk density of this devitrified glass is 2.2161 cm3/ g, water absorption rate is
0.012%。
Embodiment 3
（1）By carbide slag in high temperature Muffle furnace, 750 DEG C are raised to the heating rate of 6 DEG C/min, then with the speed of 1 DEG C/min
Rate is warmed up to 1100 DEG C and is incubated 100min, then cools to room temperature with the furnace and obtain the raw material rich in CaO, and wherein CaO content is
88.67wt%；
（2）By step（1）The raw material rich in CaO that obtains and rich in SiO2Auxiliary material, rich in Al2O3Auxiliary material and be rich in
Na2CO3Auxiliary material mix after 110min in mixer, being placed in alumina crucible makes it melt in high temperature Muffle furnace.It is rich in
The raw material of CaO accounts for the 53wt% of raw material total amount, rich in SiO2Auxiliary material account for the 40.21wt% of raw material total amount（Quartz sand, wherein SiO2
Content is 95wt%）, rich in Al2O3Auxiliary material account for the 2.13wt% of raw material total amount（Bauxite, wherein Al2O3Content is 90wt%）,
Rich in Na2CO3Auxiliary material account for the 5.36wt% of raw material total amount（Soda ash, wherein Na2CO3Content is 80wt%）.It is incubated at 1450 DEG C
Carry out being made annealing treatment at thermal state forming is placed in 600 DEG C after 90min.Obtain crystallite glass through a series of process of glass-ceramic processes again
Glass.
Using the bulk density of Archimedes method determination sample, foundation《Expectation of Glass-Ceramics Used as Decorated Materials JC/T872-
2000》, determine the water absorption rate of sample.As a result show, the bulk density of this devitrified glass is 2.3464 cm3/ g, water absorption rate is
0.042%。
Embodiment 4
（1）By carbide slag in high temperature Muffle furnace, 800 DEG C are raised to the heating rate of 5 DEG C/min, then with the speed of 3 DEG C/min
Rate is warmed up to 1000 DEG C and is incubated 150min, then cools to room temperature with the furnace and obtain the raw material rich in CaO, and wherein CaO content is
89.75wt%；
（2）By step（1）The raw material rich in CaO that obtains and rich in SiO2Auxiliary material, rich in Al2O3Auxiliary material and be rich in
Na2CO3Auxiliary material mix after 120min in mixer, being placed in alumina crucible makes it melt in high temperature Muffle furnace.It is rich in
The raw material of CaO accounts for the 54.26wt% of raw material total amount, rich in SiO2Auxiliary material account for the 34.93wt% of raw material total amount（Quartz sand, wherein
SiO2Content is 99wt%）, rich in Al2O3Auxiliary material account for the 4.52wt% of raw material total amount（Bauxite, wherein Al2O3Content is
83wt%）, rich in Na2CO3Auxiliary material account for the 6.29wt% of raw material total amount（Washing soda, wherein Na2CO3Content is 85wt%）.
Being incubated at 1375 DEG C after 135min carries out being made annealing treatment at thermal state forming is placed in 630 DEG C.Again through a series of glass-ceramic processes
Process obtains devitrified glass.
Using the bulk density of Archimedes method determination sample, foundation《Expectation of Glass-Ceramics Used as Decorated Materials JC/T872-
2000》, determine the water absorption rate of sample.As a result show, the bulk density of this devitrified glass is 2.1365 cm3/ g, water absorption rate is
0.0063%。
Embodiment 5
（1）By carbide slag in high temperature Muffle furnace, 700 DEG C are raised to the heating rate of 7 DEG C/min, then with the speed of 2 DEG C/min
Rate is warmed up to 1100 DEG C and is incubated 130min, then cools to room temperature with the furnace and obtain the raw material rich in CaO, and wherein CaO content is
91.50wt%；
（2）By step（1）The raw material rich in CaO for obtaining and auxiliary material are rich in SiO2Auxiliary material, rich in Al2O3Auxiliary material and be rich in
Na2CO3Auxiliary material mix after 100min in mixer, being placed in alumina crucible makes it melt in high temperature Muffle furnace.It is rich in
The raw material of CaO accounts for the 55wt% of raw material total amount, rich in SiO2Auxiliary material account for the 34.86wt% of raw material total amount（Quartz sand, wherein SiO2
Content is 98wt%）, rich in Al2O3Auxiliary material account for the 3.29wt% of raw material total amount（Bauxite, wherein Al2O3Content is 90wt%）,
Rich in Na2CO3Auxiliary material account for the 6.85wt% of raw material total amount（Soda, wherein Na2CO3Content is 90%）.It is incubated at 1425 DEG C
Carry out being made annealing treatment at thermal state forming is placed in 620 DEG C after 105min.Obtain crystallite through a series of process of glass-ceramic processes again
Glass.
Using the bulk density of Archimedes method determination sample, foundation《Expectation of Glass-Ceramics Used as Decorated Materials JC/T872-
2000》, determine the water absorption rate of sample.As a result show, the bulk density of this devitrified glass is 2.1041 cm3/ g, water absorption rate is
0.027%。
Claims (5)
1. a kind of method that utilization carbide slag prepares devitrified glass, is carried out as follows：
（1）Carbide slag is once warming up to 700 ~ 800 DEG C, secondary temperature elevation is to 1000 ~ 1100 DEG C and is incubated 90 ~ 150min, then cold
But the raw material rich in CaO is obtained to room temperature；
（2）By step（1）The raw material rich in CaO that obtains and rich in SiO2Auxiliary material, rich in Al2O3Auxiliary material and rich in Na2CO3
Auxiliary material be sufficiently mixed after, melting, and be incubated at 1350-1450 DEG C after 90-150min and carry out thermal state forming is placed in 600-
Make annealing treatment at 650 DEG C, then devitrified glass is obtained through glass-ceramic process.
2. method according to claim 1, it is characterised in that：Step（1）Heating rate is 5 ~ 7 DEG C/min；It is secondary
Heating rate is 1 ~ 3 DEG C/min.
3. method according to claim 1, it is characterised in that：Step（1）CaO content in the obtained raw material rich in CaO
≥80wt%。
4. method according to claim 1, it is characterised in that：Raw material rich in CaO accounts for 40 ~ 55wt% of raw material total amount, rich
Containing SiO2Auxiliary material account for 34 ~ 55wt% of total amount, rich in Al2O3Auxiliary material account for 2 ~ 5wt% of total amount, rich in Na2CO3Auxiliary material account for always
3 ~ 7wt% of amount.
5. the method according to claim 1 or 4, it is characterised in that：Rich in SiO2Auxiliary material be quartz sand, wherein SiO2Contain
Amount >=75wt%；Rich in Al2O3Auxiliary material be bauxite, wherein Al2O3Content >=80wt%；Rich in Na2CO3Auxiliary material is soda, stone
One kind in alkali, soda ash, washing soda, wherein Na2CO3Content >=70wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110997579A (en) * | 2017-06-30 | 2020-04-10 | Arc法国公司 | Production of glass from a mixture comprising calcium oxide, and glass furnace |
| US11591247B2 (en) | 2017-05-23 | 2023-02-28 | Arc France | Combined furnace |
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| CN1958499A (en) * | 2006-09-28 | 2007-05-09 | 贵州省遵义碱厂 | Heat preservation insulator of xonaltite, and preparation method |
| CN101805128A (en) * | 2010-04-20 | 2010-08-18 | 香港福山实业有限公司 | Jade-type glass-ceramic and preparation method thereof |
| CN102206045A (en) * | 2010-03-31 | 2011-10-05 | 徐州康腾微晶玻璃制品科技有限公司 | Black microcrystalline glass and manufacturing method thereof |
| CN105731808A (en) * | 2016-04-20 | 2016-07-06 | 昆明理工大学 | Method for preparing glass ceramics |
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| CN1958499A (en) * | 2006-09-28 | 2007-05-09 | 贵州省遵义碱厂 | Heat preservation insulator of xonaltite, and preparation method |
| CN102206045A (en) * | 2010-03-31 | 2011-10-05 | 徐州康腾微晶玻璃制品科技有限公司 | Black microcrystalline glass and manufacturing method thereof |
| CN101805128A (en) * | 2010-04-20 | 2010-08-18 | 香港福山实业有限公司 | Jade-type glass-ceramic and preparation method thereof |
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| US11591247B2 (en) | 2017-05-23 | 2023-02-28 | Arc France | Combined furnace |
| CN110997579A (en) * | 2017-06-30 | 2020-04-10 | Arc法国公司 | Production of glass from a mixture comprising calcium oxide, and glass furnace |
| CN110997579B (en) * | 2017-06-30 | 2022-08-09 | Arc法国公司 | Production of glass from a mixture comprising calcium oxide, and glass furnace |
| US11807567B2 (en) | 2017-06-30 | 2023-11-07 | Arc France | Production of glass from a mixture comprising calcium oxide, and glass furnace |
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