CN1024652C - Nucleated glass made from tungsten slag and prep. thereof - Google Patents
Nucleated glass made from tungsten slag and prep. thereof Download PDFInfo
- Publication number
- CN1024652C CN1024652C CN 91100652 CN91100652A CN1024652C CN 1024652 C CN1024652 C CN 1024652C CN 91100652 CN91100652 CN 91100652 CN 91100652 A CN91100652 A CN 91100652A CN 1024652 C CN1024652 C CN 1024652C
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- glass
- tungsten
- preparation
- fluorite
- tungsten slag
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- 239000011521 glass Substances 0.000 title claims abstract description 57
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 39
- 239000010937 tungsten Substances 0.000 title claims abstract description 39
- 239000002893 slag Substances 0.000 title claims abstract description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 34
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 17
- 239000010433 feldspar Substances 0.000 claims abstract description 15
- 239000010436 fluorite Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims description 31
- 230000008025 crystallization Effects 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 235000017550 sodium carbonate Nutrition 0.000 claims description 16
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002367 phosphate rock Substances 0.000 claims description 10
- 239000006093 Sitall Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 6
- 238000007497 glass batching Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000006132 parent glass Substances 0.000 claims description 5
- 238000010309 melting process Methods 0.000 claims description 3
- 239000000289 melt material Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 235000019738 Limestone Nutrition 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000004566 building material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000006028 limestone Substances 0.000 abstract 1
- 239000004579 marble Substances 0.000 abstract 1
- 239000010446 mirabilite Substances 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000004927 fusion Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910004762 CaSiO Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910001678 gehlenite Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- -1 fluorochemical Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C03C10/16—Halogen containing crystalline phase
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (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)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to tungsten slag microcrystalline glass and a preparation method thereof. The glass comprises 50 to 60% of concentration tailing of tungsten ore exploitation as a principal raw material, 35 to 45% of limestone, 2 to 10% of feldspar, 3 to 5% of sodium carbonate and 1 to 2% of mirabilite, and also comprises 6 to 9% of the formula total content of fluorite, or 4 to 6% of fluorite and 10 to 14% of phosphorus ore, and through melting, forming and heat treating, a new material with the characteristics of both glass and ceramics is prepared. The present invention has the advantages of conversion of waste into building materials, utilization of secondary resources, solution of the problem of environmental pollution, similar appearance of the prepared microcrystalline glass to marble and low cost.
Description
The present invention relates to a kind of devitrified glass ceramics.
At present cinder microcrystalline glass is to be main raw material with metallurgical slag, solid fuel, lime-ash etc., add other an amount of frit and necessary nucleator, through fusing, moulding, thermal treatment after and a kind of type material that has glass and ceramic characteristics concurrently of formation.Having introduced a kind of in English Patent (BP986289) is the devitrified glass of raw material with the metallurgical slag, and its composition range is SiO
245～65%, CaO 15～45%, Al
2O
35～30%, MgO 5%, and the nucleus agent comprises transition element oxide compound, fluorochemical, phosphoric acid salt or its mixture, compound, open hearth slag, bone ash or fuel ash.It is the devitrified glass of raw material that Japanese Patent (39-1024) has been introduced with the blast furnace slag, and its composition range is SiO
240～70%, Al
2O
35～15%, CaO 13～35%, MgO 2～12%, Na
2O 2～12%, nucleus agent fluorite, potassium bichromate, phosphoric acid.The existing tungsten ore tailings of China is about more than 1,000 ten thousand tons, and annual also with 400,000 tons speed increase, and these slags also do not obtain utilizing at present, be not only the huge waste on the resource, and environment is also done great damage.
The objective of the invention is to utilize the tailings of exploitation tungsten ore ore dressing discharging as the main material production tungsten slag sitall.
Purpose of the present invention can realize by following measure: a kind of preparation method of tungsten slag sitall, the chemical ingredients of this glass is: SiO
246.7 Al～56.2%,
2O
38.3～11%, CaO 20～25.2%, MgO 0.7～2.5%, Na
2O 3.2～4.2%, K
2O 2～2.6%, Fe
2O
30.8 CaF～1.1%,
20.5 P～3.5%,
2O
50.8～4.3%, it is characterized in that: the preparation method of above-mentioned glass is:
(1) get the tailings of 50%～60% following Chemical Composition exploitation tungsten ore ore dressing:
SiO
276.2～86.3% Al
2O
37.4～8.4%
CaO 0.2～1.3% MgO 0.02～0.8%
K
2O 2.0～2.8% Na
2O 1.04～2.02%
Fe
2O
30.9～1.6% MnO 0.007～0.09%
CaF
20.4～0.53% P
2O
50.05～0.73%
WO
30.01～0.062%
And 35～45% Wingdale, 2～10% feldspar, 3～5% soda ash, 1～2% saltcake, also have the fluorite of above-mentioned prescription total amount 6～9% or the Rock Phosphate (72Min BPL) of 4～6% fluorites and 10～14%, each component mixes after crossing 40 mesh sieves,
(2) be that 1450～1520 ℃ of High Temperature Furnaces Heating Apparatuss all melt material in temperature,
(3) glass metal that melting process is obtained was handled 2～6 hours 650～720 ℃ of temperature coring after moulding,
(4) glass after the coring processing was handled 1～6 hour through 850～1050 ℃ of crystallization again.
Preferably the parent glass batching is tungsten slag 55%, feldspar 5%, Wingdale 40%, soda ash 4%, saltcake 1.5%.Nucleus, coring are to handle 2～4 hours at 680～700 ℃, and crystallization is to handle 2～4 hours at 900～1000 ℃.
Tungsten slag sitall is that the tailings that produces when utilizing the ore dressing of exploitation tungsten ore is made main raw material, and be aided with other raw materials such as feldspar, Wingdale with fusing assistant, nucleus agent melt, moulding, after coring and crystallization are handled, make again.Its outward appearance of the used tungsten slag of the present invention raw material is particulate state, diameter Distribution: be 2 millimeters to the maximum, content is less than 10%; Minimum is 0.07 millimeter, and content is less than 10%; 0.5～0.6 millimeter of average out to, content are 80%.The scoriaceous essential mineral of tungsten is α-SiO mutually
2, albite (Na[AlSi
3O
8]) or (Na, and Ca) (Si, Al)
4O
8, also have a spot of wolframite [(Mn, Fe) (WO
4)] and sheelite [Ca(WO
4)].This scoriaceous chemical ingredients scope is:
SiO
276.2～86.3% Al
2O
37.4～8.4%
CaO 0.2～1.3% MgO 0.02～0.8%
K
2O 2.0～2.8% Na
2O 1.04～2.02%
Fe
2O
30.9～1.6% MnO 0.007～0.09%
CaF
20.4～0.53% P
2O
50.05～0.73%
WO
30.01～0.062%
Its consumption is 50～60%, if then can not form devitrified glass outside this scope.Preferably the consumption of tungsten tailings makes the glass that makes have flowability 55%, and viscosity is little, the optimum regime that bubble and scum silica frost are all few.
Another kind of raw material of the present invention is a feldspar, and its chemical ingredients is: SiO
266%, Al
2O
317%, Fe
2O
30.5%, Na
2O 14%, and consumption is generally 5～10%.When consumption surpasses 10%, the fusing difficulty.When consumption is lower than 5%, more serious to the refractory corrosion in the High Temperature Furnaces Heating Apparatus, and the glass metal devitrification.Best felspathic consumption is 5%.
It is Wingdale that the present invention also has a kind of raw material, and its chemical ingredients scope is CaO 〉=49%, MgO 〉=3%, Fe
2O
3≤ 0.25%, consumption generally is 35～45%.When its consumption was low, glass did not produce crystallization.The violent devitrification of glass when its consumption is higher, preferably the consumption of Wingdale is 40%.
The fusing assistant that the present invention adopts is soda ash and saltcake, when adding the soda ash amount when very few, the glass melting difficulty, viscosity increases, but when the soda ash amount of adding is higher than 5% the glass metal devitrification, thereby the consumption of soda ash is generally 3～5%, preferably 4%.The add-on of general saltcake is 1～2%, and when the add-on of saltcake was higher than 2%, the flash phenomenon can take place in fusing, but when the saltcake amount adds saltcake very little or not, again can be because of SiO
2Surplus scum silica frost occurs on fusion glass liquid surface, and preferably the add-on of saltcake is 1.5%.
For making product obtain reasonable integrally crystallization, thereby need to add suitable nucleus agent, nucleus agent of the present invention is fluorite and ground phosphate rock.The main component of fluorite is CaF
2, content is about 83.96%.When it used separately, consumption was that the parent glass batching is the raw material and 6～9% of the dosage sum of fluxing.Can not fine nucleation when consumption is low, be unfavorable for that when consumption is higher devitrified glass generates, optimum amount is 6～7%.Crystalline phase by the resulting tungsten ore slag of fluorite nucleus agent crystallite glass is wollastonite (CaSiO
3) and gehlenite [Ca, Al(Al, Si
4O
7)].Can be P also with fluorite and main component
2O
5Content share about 37.46% Rock Phosphate (72Min BPL), and this moment, the fluorite consumption was 4～6% of a parent glass batching, and the Rock Phosphate (72Min BPL) consumption then is 10-14, and its optimum amount is that fluorite is 5～6%, and Rock Phosphate (72Min BPL) is 11～12%.Crystalline phase by these two kinds of resulting tungsten slag sitalls of nucleus agent is wollastonite (CaSiO
3), gehlenite [(Ca, Al(Al, Si
4O
7) and phosphatic rock [Ca
5(PO
4)
3].
Preparation technology's process description of tungsten slag sitall is as follows among the present invention:
1450～1520 ℃ 650～720 ℃ 850～1050 ℃ of raw materials
Fusing assistant → fusing → moulding → coring → crystallization
Nucleus agent 2～6 hours 1～6 hour
At first be that various raw materials, fusing assistant and nucleus agent are weighed by the quantity of prescription regulation, wherein various components all need be passed through 40 mesh sieves, behind uniform mixing, put into High Temperature Furnaces Heating Apparatus, in air, melt, its temperature of fusion generally 1450～1520 ℃ make material all fusing do not have ore particle to exist till.The no bubble that melting process is obtained, the glass metal of no sand grains carry out coring and crystallization and thermal treatment again after moulding.Coring thermal treatment is to handle 2～6 hours down at 650～720 ℃.The fast nucleus quantity of nucleating growth speed is many in this temperature range, and too short as the time, the quantity of nucleus is unfavorable for crystallization less; Otherwise nucleation time is long, and nucleus quantity not only no longer increases, and is transformed into chain but also nucleus can take place, and preferably handles 2～4 hours at 680～700 ℃.Coring is carried out crystallization and thermal treatment after handling again, and it is to handle 1～6 hour at 850～1050 ℃, and percent crystallization in massecuite is very low when crystallization temperature is low, but crystal was thick plate when crystallization temperature was too high, percent crystallization in massecuite changes not remarkable, and microhardness descends, so optimum crystallization temperature is 900～1000 ℃.Crystallization time is too short, and it is meticulous to separate out crystal; Crystallization time is long, and percent crystallization in massecuite changes not remarkable, and crystal grain is excessive, and microhardness has decline slightly, and therefore best crystallization time is 2～4 hours.
The chemical ingredients of the tungsten slag microcrystalline glass that is made by aforesaid method is: SiO
246.7 Al～58.1%,
2O
38.3～12.7%, CaO 20～25.5%, MgO 0.7～2.9%, Na
2O 3.2～4.7%, K
2O 2～2.6%, Fe
2O
30.8 CaF～1.1%,
20.5 P～3.5%,
2O
50.3～4.7%.
The salient features scope of tungsten slag microcrystalline glass of the present invention is as follows: density 2.6-2.725g/cm
3, microhardness 568～766kg/mm
2, linear expansivity 78.0～80 * 10
-7℃
-1, water tolerance (the 0.01NHCl milliliter number that consumes in titration) 0.15～0.20.
Example 1
Get 47.6 parts of tungsten ore slags, 9.5 parts of feldspars, 38.1 parts of Wingdales, 2.9 parts of soda ash, 1.9 parts of saltcake, other adds the agent of 6 parts of fluorite nucleus, more than after each raw material all crosses 40 mesh sieves, uniform mixing places in the melting furnaces, be fused into the uniform glass of no bubble, no sand grains under 1500 ℃, this moment, the glass analysis of components was as follows:
SiO
254.95% Al
2O
310.58% CaO, 22.66% MgO, 2.76% Na
2O 4.27% K
2O 2.20% Fe
2O
31.01% CaF
21.10% P
2O
50.32% WO
3＜0.01% treat the glass metal moulding after, send into and carry out coring, crystallization and thermal treatment in the heat treatment kiln, coring was handled 2 hours when 680 ℃ of temperature, crystallization was handled 2 hours in the time of 900 ℃ again, obtaining outward appearance is linen devitrified glass, density 2.69g/cm
3, microhardness 710.2kg/mm
2, linear expansivity 80.1 * 10
-7℃
-1
Example 2
Get 52.1 parts of tungsten ore slags, 4.7 parts of feldspars, 37.9 parts of Wingdales, 3.8 parts of soda ash, 1.4 parts of saltcake, other adds the agent of 7 parts of fluorite nucleus.By example 1 operation, 1500 ℃ of fusings down, the analysis of components of gained glass is as follows:
SiO
257.58% Al
2O
38.31% CaO, 22.47% MgO, 2.25% Na
2O 4.16% K
2O 2.40% Fe
2O
31.07% CaF
21.13% P
2O
50.58% WO
3＜0.01% treats after the glass ware forming, sends into and carries out coring, crystallization and thermal treatment in the heat treatment kiln.Coring was handled 2 hours when 685 ℃ of temperature, after coring is handled, handled 2 hours 950 ℃ of crystallization again, obtained the devitrified glass of appearance off-white, density 2.711g/cm
3, microhardness 766.1kg/mm
2, linear expansivity 78.5 * 10
-7℃
-1
Example 3
Get 56.6 parts of tungsten ore slags, 4.7 parts, 33.0 parts Wingdales of feldspar, 4.7 parts of soda ash, 0.94 part of saltcake, other adds the agent of 9 parts of fluorite nucleus, repeats example 1 operation, 1520 ℃ of melting furnace temperatures, and gained glass analysis of components is as follows:
SiO
258.04% Al
2O
38.52% CaO 21.43% MgO 2.07% Na
2O 4.66% K
2O 2.01% Fe
2O
31.05% CaF
21.63% P
2O
50.57% WO
3＜0.01%。Treat to send into behind the glass ware forming and carry out coring in the heat treatment kiln and crystallization is handled, when 685 ℃ of temperature, handled 2 hours, in the time of 950 ℃, handled 2 hours again, obtain the appearance off-white devitrified glass, density 2.723g/cm
3, microhardness 723.3kg/mm
2, linear expansivity is 79.3 * 10
-7℃
-1
Example 4
Get 47.40 parts of tungsten ore slags, 4.7 parts of feldspars, 42.7 parts of Wingdales, 3.8 parts of soda ash, 1.4 parts of saltcake, other adds the agent of 6 parts of fluorite nucleus, repeats example 1 operation, 1500 ℃ of fusings down of melting furnace temperature, and the analysis of components of glass is as follows:
SiO
254.30% Al
2O
38.43% CaO 25.46% MgO 2.86% Na
2O 3.65% K
2O 2.13% Fe
2O
31.00% CaF
21.01% P
2O
50.35% WO
3＜0.01%。After treating the glass metal moulding, send into and carry out coring, crystallization and thermal treatment in the heat treatment kiln.Coring was handled 3 hours when 720 ℃ of temperature, and crystallization 4 hours in the time of 1000 ℃ obtains the appearance off-white devitrified glass, density 2.72g/cm again
3, microhardness 700.2kg/mm
2, linear expansivity is 81.0 * 10
-7℃
-1
Example 5
Get 52.1 parts of tungsten ore slags, 4.7 parts of feldspars, 37.9 parts of Wingdales, 3.8 parts of soda ash, 1.4 parts of saltcake, other adds 4 parts of fluorites and the agent of 14 parts of ground phosphate rock nucleus, by example 1 operation, and 1480 ℃ of temperature of fusion, the analysis of components of gained glass is as follows:
SiO
246.77% Al
2O
312.64% CaO 25.45% MgO 0.72% Na
2O 3.29% K
2O 2.02% Fe
2O
30.84% CaF
23.23% P
2O
54.67% WO
3＜0.01%。Treat to send into behind the glass ware forming and carry out coring, crystallization and thermal treatment in the heat treatment kiln.Handled 2 hours in 685 ℃ of coring of temperature, crystallization 2 hours in the time of 950 ℃ obtains the appearance off-white devitrified glass, density 2.681g/cm again
3, microhardness 700kg/mm
2, linear expansivity 86.6 * 10
-7℃
-1
Example 6
Get 52.1 parts of tungsten ore slags, 4.7 parts of feldspars, 37.9 parts of Wingdales, 3.8 parts of soda ash, 1.4 parts of saltcake, other adds 6 parts of fluorites and the agent of 10 parts of ground phosphate rock nucleus, by example 1 operation, and 1450 ℃ of temperature of fusion, the analysis of components of gained glass is as follows:
SiO
246.87%、Al
2O
312.54%、CaO 25.5%、MgO 0.74%、Na
2O 3.28%、K
2O 2.0%、Fe
2O
30.90%、CaF
23.10%、P
2O
54.55%、WO
3＜0.01%。Treat to send into behind the glass ware forming and carry out coring, crystallization and thermal treatment in the heat treatment kiln.Handled 4 hours in 685 ℃ of coring of temperature, crystallization was handled 4 hours in the time of 950 ℃ again, obtained the appearance off-white devitrified glass, density 2.682g/cm
3, microhardness 700.5kg/mm
2, linear expansivity 86.8 * 10
-7℃
-1
50～60% is the tungsten ore tailings in the raw material of the present invention, the waste residue of discharging when it is the tungsten ore ore dressing, and its secondary resource that rationally is utilized as the tungsten slag utilizes the approach opened up again.Feldspar, Wingdale are the raw materials of factory's fusion cast glass, and price is low, supply is sufficient.Therefore be that the cost of main material production devitrified glass is low with tungsten slag, feldspar, Wingdale.Contain Na in the tungsten slag
2O, K
2The O(summation is 3～4.5%) only need add a spot of fusing assistant soda ash when making molten glass and get final product, save a large amount of soda ash, and the glass metal clarification is good.General high slag microcrystallite glass is a Vandyke brown, needs to add discoloring agent and can produce shallow white micro-crystals glass.And the tungsten slag microcrystalline glass need not to add discoloring agent, can direct production go out the light gray-white devitrified glass, reaches the effect of parian.
(annotate: the per-cent in the present specification all is weight percentage)
Claims (5)
1, a kind of preparation method of tungsten slag sitall, the chemical ingredients of this glass is: SiO
246.7 Al～58.1%,
2O
38.3～12.7%, CaO20～25.5%, MgO0.7～2.9%, Na
2O3.2～4.7%, K
2O2～2.6%, Fe
2O
30.8 CaF～1.1%,
20.5 P～3.5%,
2O
50.3～4.7%, it is characterized in that: the preparation method of above-mentioned glass is:
(1) get the tailings of 50%～60% following Chemical Composition exploitation tungsten ore ore dressing:
SiO
276.2～86.3% Al
2O
37.4～8.4%
CaO 0.2～1.3% MgO 0.02～0.8%
K
2O 2.0～2.8% Na
2O 1.04～2.02%
Fe
2O
30.9～1.6% MnO 0.007～0.09%
CaF
20.4～0.53% P
2O
50.05～0.73%
WO
30.01～0.062%
And 35～45% Wingdale, 2～10% feldspar, 3～5% soda ash, 1～2% saltcake, also have the fluorite of above-mentioned prescription total amount 6～9% or the Rock Phosphate (72Min BPL) of 4～6% fluorites and 10～14%, each component mixes after crossing 40 mesh sieves,
(2) be that 1450～1520 ℃ of High Temperature Furnaces Heating Apparatuss all melt material in temperature,
(3) glass metal that melting process is obtained was handled 2～6 hours 650～720 ℃ of temperature coring after moulding,
(4) glass after the coring processing was handled 1～6 hour through 850～1050 ℃ of crystallization again.
2, the preparation method of tungsten slag sitall according to claim 1 is characterized in that: the parent glass batching is tungsten slag 55%, feldspar 5%, Wingdale 40%, soda ash 4%, saltcake 1.5%.
3, the preparation method of tungsten slag sitall according to claim 1 and 2, it is characterized in that: consumption was 6～7% of a parent glass batching sum when nucleus agent fluorite was used separately, when nucleus agent fluorite and Rock Phosphate (72Min BPL) share, the fluorite consumption was 5～6%, the Rock Phosphate (72Min BPL) consumption is 11～12%.
4, the preparation method of tungsten slag sitall according to claim 3 is characterized in that: coring is to handle 2～4 hours at 680～700 ℃.
5, the preparation method of tungsten slag sitall according to claim 4 is characterized in that: crystallization is to handle 2～4 hours at 900～1000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100652 CN1024652C (en) | 1991-01-29 | 1991-01-29 | Nucleated glass made from tungsten slag and prep. thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100652 CN1024652C (en) | 1991-01-29 | 1991-01-29 | Nucleated glass made from tungsten slag and prep. thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063853A CN1063853A (en) | 1992-08-26 |
| CN1024652C true CN1024652C (en) | 1994-05-25 |
Family
ID=4904754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91100652 Expired - Fee Related CN1024652C (en) | 1991-01-29 | 1991-01-29 | Nucleated glass made from tungsten slag and prep. thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024652C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383072C (en) * | 2004-08-12 | 2008-04-23 | 李章大 | Microcrystalline glass produced from molybdenum containing gangue and its method |
| CN103011601B (en) * | 2012-12-05 | 2016-04-27 | 毛庆云 | A kind of take quartz sand as devitrified glass of major ingredient and preparation method thereof |
| CN103232158B (en) * | 2013-05-09 | 2015-09-30 | 南京师范大学 | A kind of complex ore slag glass flux composition and application thereof |
| CN103951193B (en) * | 2014-05-08 | 2016-02-24 | 中国科学院过程工程研究所 | A kind of nickel-molybdenum ore selects smelting tailing microcrystal glass and preparation method thereof |
| CN104926134A (en) * | 2015-06-01 | 2015-09-23 | 安徽省益民工贸集团有限公司 | Acid and alkali corrosion-resistant glass ceramic plate and preparation method for same |
| CN108585509A (en) * | 2018-04-27 | 2018-09-28 | 南昌大学 | A kind of devitrified glass preparation method |
| CN109865734A (en) * | 2019-03-13 | 2019-06-11 | 兰州有色冶金设计研究院有限公司 | A method of vitreum is produced using chemical industry abraum salt |
-
1991
- 1991-01-29 CN CN 91100652 patent/CN1024652C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1063853A (en) | 1992-08-26 |
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