CN105060717B - It is a kind of using molybdic tailing as building decorative glass ceramics of main material and preparation method thereof - Google Patents
It is a kind of using molybdic tailing as building decorative glass ceramics of main material and preparation method thereof Download PDFInfo
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Abstract
The present invention proposes a kind of using molybdic tailing as building decorative glass ceramics of main material and preparation method thereof, includes following steps：1) following component is taken：Molybdic tailing, quartz sand, aluminium oxide, lime stone, soda ash, zinc oxide, barium carbonate, boric acid, antimony oxide, cerium oxide, sodium nitrate；2) glass batch of gained is fused into glass metal；3) gained glass metal is made to flow into ball press, regular shape, the glass ball particle of uniform particle sizes is made；4) glass particle is subjected to controlled micro crystallization, cut, polish to get.Compared with product, the present invention has the following advantages for the present invention and the prior art：1. technique is simple, ripe, finished product rate qualification rate is improved.2. improving tailing dosage in proportioning, production cost is reduced, product newly energy and value is improved, expands its purposes range, increase benefit.3. having developed devitrified glass production technology and technology, tailing microcrystal glass new product is increased.
Description
Technical field
The present invention proposes a kind of using molybdic tailing as building decorative glass ceramics of main material and preparation method thereof, and content relates to
And the fields such as utilization of waste as resource.
Technical background
Devitrified glass is a kind of polycrystalline material as obtained from the crystallization for controlling glass.Devitrified glass has been formed at present
A kind of material of special class, various in style, different properties have very extensive purposes.It is high, wear-resistant with intensity
It damages, corrosion-resistant, weather resistance, absorb water, the excellent physicochemical property such as cleaning convenience, "dead" pollution；Its tone simultaneously
Uniformly, the beneficial appearance characteristics such as gloss is soft sparkling and crystal-clear, and surface compact is had no time.Since devitrified glass various aspects of performance is superior to day
Right stone material is specialized in so being widely used in all kinds of building and ornament materials now in engineering.
The raw material of production devitrified glass are substantially industrial chemicals in addition to quartz sand, lime stone at present, lead to crystallite glass
Glass production cost is higher.Molybdic tailing discharges, and the solid or powdery that cannot be temporarily utilized after exploitation, sorting ore
Waste material, including Molybdenum Mine tailing and plant tailing, wherein mill tailings includes the association country rock produced and midway is rejected
Poor value；Plant tailing includes the mineral waste (tailing) discharged later using certain technique, mechanical washing ore, this
A little tailings are piped to Tailings Dam storage.For this purpose, molybdic tailing overwhelming majority in China's accumulates in Tailings Dam, stream and original for a long time
Open countries etc. are without being used effectively.It occupies a large amount of soils, pollution environment, forms potential geological disaster.
Mill tailings the like waste is the important carrier of heavy metal and other harmful elements, to earth's surface soil and groundwater
Quality has a significant impact, and can not be ignored.It is constantly promoted for this purpose, being exploited with molybdenum ore, influence of the molybdic tailing to environment and society
Aggravating, along with the cave-in accident of Tailings Dam is multiple, very big shadow is caused to people's lives, national product and economic development
It rings.It is molybdenum ore exploitation enterprise social problem urgently to be resolved hurrily rationally to make full use of molybdic tailing.
In recent years, with the increase of molybdenum in China yield, the molybdenum deep processing ability in China also has certain scale, and establish
The molybdenum product that one batch facility is advanced, strong technical strength, molybdenum alloy, the scientific research of molybdenum chemical industry, manufacturer.But molybdenum ore is through essence
A large amount of discharges of generated mine tailing, huge pressure is brought to social development and environmental protection after choosing.China's molybdic tailing
In chemical composition mainly include：Silica, alundum (Al2O3), di-iron trioxide, calcium oxide, magnesia and potassium oxide etc.,
The total amount of these oxides accounts for most of more than the 95wt% of entire molybdic tailing oxide components, more than ingredient to prepare building dress
Adorn the when utilizable oxide of devitrified glass.
Utilization for tailing, it is main in the past to concentrate to produce mixing for cement and silicate product, glass, ceramics
Material, dosage is few, and quality requirements are high, 1,000,000,000 tons of this huge numbers are up to for discarded tailing and waste annual emissions and
Speech, utilization rate is very low, is not enough to elimination molybdenum ore enterprise and is seriously affected caused by environment.It is prepared using molybdic tailing
High quality, the construction material of high added value or building and ornament materials, the warp for the enterprise that molybdic tailing can not only be turned waste into wealth, increased
Ji benefit can also improve the use of molybdic tailing, mitigate environmental pressure, realize environmental-friendly.
Invention content
The technical problems to be solved by the invention are to propose one kind using molybdic tailing as main material for the above-mentioned prior art
Building decorative glass ceramics and preparation method thereof, it can be achieved that comprehensive utilization to molybdic tailing.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of building using molybdic tailing as main material fills
Devitrified glass is adornd, in parts by mass, raw material includes following component：35-48 parts of molybdic tailing, 18-22 parts of quartz sand, aluminium oxide 2-
3 parts, 15-19 parts of lime stone, 5-7 parts of soda ash, 1-3 parts of zinc oxide, 6-7 parts of barium carbonate, 1-3 parts of boric acid, antimony oxide 0-1
Part, 0.1-0.5 parts of cerium oxide, 0.1-0.2 parts of sodium nitrate.
It is described using molybdic tailing as the preparation method of the building decorative glass ceramics of main material, it is characterised in that include with
Lower step：
1) in terms of mass parts, following component is taken：35-48 parts of molybdic tailing, 18-22 parts of quartz sand, 2-3 parts of aluminium oxide, lime
15-19 parts of stone, 5-7 parts of soda ash, 1-3 parts of zinc oxide, 6-7 parts of barium carbonate, 1-3 parts of boric acid, 0-1 parts of antimony oxide, cerium oxide
0.1-0.5 parts, 0.1-0.2 parts of sodium nitrate；
2) glass batch of gained is fused into glass metal, melting condition is：1500-1550 DEG C of fusion temperature, heat preservation
8-12 hours；
3) gained glass metal is made to flow into ball press, regular shape, the glass ball particle of uniform particle sizes is made；
4) glass particle is subjected to controlled micro crystallization, temperature increasing schedule is：From room temperature to 800 DEG C of temperature sections, heating rate 4-6
DEG C/min, 800 DEG C to the crystallization temperature point finally set, heating rate is 1-3 DEG C/min, crystallization temperature 1130-1180
DEG C, keep the temperature 1-3 hour, then with 2-5 DEG C/min of rate of temperature fall be cooled to 100 DEG C hereinafter, cut, polish to get.
By said program, the particle size range of the glass ball particle described in step 3) is：2-4mm.
By said program, further include and glass ball particle obtained in step 3) is laid in carry out table in refractory-material dies
The ceramic pigment prepared using ceramic slurry glaze flush coater, is equably sprayed to the surface of glass marble by surface treatment.
Devitrified glass prepared by the present embodiment has plate face size big, and pure color, glossiness is high, and density and intensity are big
The characteristics of, density 2.78-2.9g/cm3, flexural strength is up to 80-120MPa.
Compared with product, the present invention has the following advantages for the present invention and the prior art：
1. technique is simple, ripe, finished product rate qualification rate is improved.
2. improving tailing dosage in proportioning, production cost is reduced, product newly energy and value is improved, expands its purposes model
It encloses, increases benefit.
3. having developed devitrified glass production technology and technology, tailing microcrystal glass new product is increased.
Specific embodiment
Technical scheme of the present invention is described in detail below by specific embodiment.
Using X Axios advanced Xray fluorescence spectrometers to the chemical composition of molybdic tailing in the present embodiment into
Row analysis, oxide components mainly include：
| Oxide components | Content (wt%) |
| SiO2 | 71.69 |
| Al2O3 | 10.42 |
| Fe2O3 | 4.38 |
| CaO | 2.40 |
| MgO | 3.06 |
| K2O | 4.84 |
| Na2O | 0.40 |
| TiO2 | 0.83 |
| SO3 | 1.33 |
| P2O5 | 0.38 |
| MnO | 0.26 |
| It is total | 100 |
More than ingredient can all be utilized by when preparing molybdic tailing building decorative glass ceramics.
Embodiment 1
It is above-mentioned using molybdic tailing as the preparation method of the devitrified glass of main material, specifically comprise the following steps：
(1) glass formula：It is a kind of using molybdic tailing as the building decorative glass ceramics of main material, in parts by mass, raw material
Including following component：35 parts of molybdic tailing, 22 parts of quartz sand, 3 parts of aluminium oxide, 19 parts of lime stone, 7 parts of soda ash, 3 parts of zinc oxide, carbon
Sour 7 parts of barium, 3 parts of boric acid, 0.8 part of antimony oxide, 0.1 part of cerium oxide, 0.1 part of sodium nitrate；
(2) preparation of glass batch：Each raw material is weighed by parts by weight in (1), is put into mixing machine after weighing well, is mixed
Close 5 minutes, you can be made mixing and glass batch；
(3) glass melting：The glass batch of gained in step (1) is fused into glass metal with glass furnace, is melted
Condition is：1500 DEG C of fusion temperature keeps the temperature 8 hours；
(4) prepared by glass marble：The glass metal of high temperature melting is introduced into diversion trench, glass ball working machine is imported into after chilly
In.Regular shape, the glass ball particle of uniform particle sizes is made.The particle size range of glass marble is：2-4mm；
(5) glass marble stone：Glass marble obtained in step (4) is laid in refractory-material dies；According to not suiting
Line requirement, glass bulb diameter are divided into respectively 2mm, 3mm, 4mm.Hereafter the glass ball surface completed is handled, utilizes pottery
Porcelain starches glaze flush coater, and the ceramic pigment prepared is equably sprayed to the surface of glass marble.It can be with shape after being sintered crystallization
It is coloured into surface, the apparent microcrystal glass plate of particle decorative pattern；
(6) crystallization of glass particle and annealing：In the glass-ceramic process of glass marble, mode of heating is uses electrical heating
Stove, the system that temperature rise period needs ensure are：From room temperature to 800 DEG C of temperature sections, heating rate be 4 DEG C/min, 800 to 1130
DEG C, heating rate is 1 DEG C/min, carries out crystallization and thermal treatment with high-temperature electric resistance furnace, crystallization temperature is 1130 DEG C, keeps the temperature 3 hours, so
Afterwards less than 100 DEG C are cooled to 2 DEG C/min of rate of temperature fall；
(7) grinding and polishing of microcrystal glass plate：Devitrified glass product obtained is ground cutting, polishing after become into
Product.
Devitrified glass prepared by the present embodiment has plate face size big, and pure color, glossiness is high, and density and intensity are big
The characteristics of, density 2.8g/cm3, flexural strength is up to 120MPa.
Embodiment 2
It is above-mentioned using molybdic tailing as the preparation method of the devitrified glass of main material, specifically comprise the following steps：
(1) glass formula：It is a kind of using molybdic tailing as the building decorative glass ceramics of main material, in parts by mass, raw material
Including following component：42 parts of molybdic tailing, 20 parts of quartz sand, 2.5 parts of aluminium oxide, 17 parts of lime stone, 6 parts of soda ash, 2 parts of zinc oxide,
6.5 parts of barium carbonate, 3 parts of boric acid, 0.5 part of antimony oxide, 0.3 part of cerium oxide, 0.2 part of sodium nitrate；
(2) preparation of glass batch：Each raw material is weighed by parts by weight in (1), is put into mixing machine after weighing well, is mixed
Close 10 minutes, you can be made mixing and glass batch；
(3) glass melting：The glass batch of gained in step (1) is fused into glass metal with glass furnace, is melted
Condition is：1530 DEG C of fusion temperature keeps the temperature 10 hours；
(4) prepared by glass marble：The glass metal of high temperature melting is introduced into diversion trench, glass ball working machine is imported into after chilly
In.Regular shape, the glass ball particle of uniform particle sizes is made.The particle size range of glass marble is：2-4mm；
(5) glass marble stone：Glass marble obtained in step (4) is laid in refractory-material dies；According to not suiting
Line requirement, glass bulb diameter are divided into respectively 2mm, 3mm, 4mm.Hereafter the glass ball surface completed is handled, utilizes pottery
Porcelain starches glaze flush coater, and the ceramic pigment prepared is equably sprayed to the surface of glass marble.It can be with shape after being sintered crystallization
It is coloured into surface, the apparent microcrystal glass plate of particle decorative pattern；
(6) crystallization of glass particle and annealing：In the glass-ceramic process of glass particle, mode of heating is uses natural gas
Heating furnace, the system that temperature rise period needs ensure are：From room temperature to 800 DEG C of temperature sections, heating rate be 5 DEG C/min, 800 to
1150 DEG C, heating rate is 1-3 DEG C/min, carries out crystallization and thermal treatment with high-temperature electric resistance furnace, crystallization temperature is 1150 DEG C, and heat preservation 2 is small
When, then less than 100 DEG C are cooled to 3.5 DEG C/min of rate of temperature fall；
(7) grinding and polishing of microcrystal glass plate：Devitrified glass product obtained is ground cutting, polishing after become into
Product.
Devitrified glass prepared by the present embodiment has plate face size big, and pure color, glossiness is high, and density and intensity are big
The characteristics of, density 2.9g/cm3, flexural strength is up to 100MPa.
Embodiment 3
It is above-mentioned using molybdic tailing as the preparation method of the devitrified glass of main material, specifically comprise the following steps：
(1) glass formula：It is a kind of using molybdic tailing as the building decorative glass ceramics of main material, in parts by mass, raw material
Including following component：48 parts of molybdic tailing, 18 parts of quartz sand, 2 parts of aluminium oxide, 15 parts of lime stone, 5 parts of soda ash, 3 parts of zinc oxide, carbon
Sour 6 parts of barium, 2 parts of boric acid, 0.3 part of antimony oxide, 0.5 part of cerium oxide, 0.2 part of sodium nitrate；
(2) preparation of glass batch：Each raw material is weighed by parts by weight in (1), is put into mixing machine after weighing well, is mixed
Close 20 minutes, you can be made mixing and glass batch；
(3) glass melting：The glass batch of gained in step (1) is fused into glass metal with glass furnace, is melted
Condition is：1550 DEG C of fusion temperature keeps the temperature 12 hours；
(4) prepared by glass marble：The glass metal of high temperature melting is introduced into diversion trench, glass ball working machine is imported into after chilly
In.Regular shape, the glass ball particle of uniform particle sizes is made.The particle size range of glass marble is：2-4mm；
(5) glass marble stone：Glass marble obtained in step (4) is laid in refractory-material dies；According to not suiting
Line requirement, glass bulb diameter are divided into respectively 2mm, 3mm, 4mm.Hereafter the glass ball surface completed is handled, utilizes pottery
Porcelain starches glaze flush coater, and the ceramic pigment prepared is equably sprayed to the surface of glass marble.It can be with shape after being sintered crystallization
It is coloured into surface, the apparent microcrystal glass plate of particle decorative pattern；
(6) crystallization of glass particle and annealing：In the glass-ceramic process of glass particle, mode of heating is uses electrical heating
Stove, the system that temperature rise period needs ensure are：From room temperature to 800 DEG C of temperature sections, heating rate be 4-6 DEG C/min, 800 to
1180 DEG C, heating rate is 3 DEG C/min, carries out crystallization and thermal treatment with high-temperature electric resistance furnace, crystallization temperature is 1180 DEG C, and heat preservation 1 is small
When, then less than 100 DEG C are cooled to 2-5 DEG C/min of rate of temperature fall；
(7) grinding and polishing of microcrystal glass plate：Devitrified glass product obtained is ground cutting, polishing after become into
Product.
Devitrified glass prepared by the present embodiment has plate face size big, and pure color, glossiness is high, and density and intensity are big
The characteristics of, density 2.78g/cm3, flexural strength is up to 80MPa.
Claims (3)
1. a kind of using molybdic tailing as the building decorative glass ceramics of main material, in parts by mass, raw material includes following component：Molybdenum
35-48 parts of tailing, 18-22 parts of quartz sand, 2-3 parts of aluminium oxide, 15-19 parts of lime stone, 5-7 parts of soda ash, 1-3 parts of zinc oxide, carbon
Sour barium 6-7 parts, 1-3 parts of boric acid, 0-1 parts of antimony oxide, 0.1-0.5 parts of cerium oxide, 0.1-0.2 parts of sodium nitrate is following
Preparation method products therefrom：There are following steps：
1) in terms of mass parts, following component is taken：35-48 parts of molybdic tailing, 18-22 parts of quartz sand, 2-3 parts of aluminium oxide, lime stone 15-
19 parts, 5-7 parts of soda ash, 1-3 parts of zinc oxide, 6-7 parts of barium carbonate, 1-3 parts of boric acid, 0-1 parts of antimony oxide, cerium oxide 0.1-
0.5 part, 0.1-0.2 parts of sodium nitrate；
2) glass batch of gained is fused into glass metal, melting condition is：1500-1550 DEG C of fusion temperature keeps the temperature 8-12
Hour；
3) gained glass metal is made to flow into ball press, regular shape, the glass ball particle of uniform particle sizes is made；
4) glass particle is subjected to controlled micro crystallization, temperature increasing schedule is：From room temperature to 800 DEG C of temperature sections, heating rate for 4-6 DEG C/
Minute, 800 DEG C to the crystallization temperature point finally set, heating rate is 1-3 DEG C/min, and crystallization temperature is 1130-1180 DEG C,
Heat preservation 1-3 hour, then with 2-5 DEG C/min of rate of temperature fall be cooled to 100 DEG C hereinafter, cut, polish to get.
It is 2. described in claim 1 using molybdic tailing as the preparation method of the building decorative glass ceramics of main material, it is characterised in that
Include following steps：
1) in terms of mass parts, following component is taken：35-48 parts of molybdic tailing, 18-22 parts of quartz sand, 2-3 parts of aluminium oxide, lime stone 15-
19 parts, 5-7 parts of soda ash, 1-3 parts of zinc oxide, 6-7 parts of barium carbonate, 1-3 parts of boric acid, 0-1 parts of antimony oxide, cerium oxide 0.1-
0.5 part, 0.1-0.2 parts of sodium nitrate；
2) glass batch of gained is fused into glass metal, melting condition is：1500-1550 DEG C of fusion temperature keeps the temperature 8-12
Hour；
3) gained glass metal is made to flow into ball press, regular shape, the glass ball particle of uniform particle sizes is made；The glass marble
The particle size range of particle is：2-4mm；
4) glass particle is subjected to controlled micro crystallization, temperature increasing schedule is：From room temperature to 800 DEG C of temperature sections, heating rate for 4-6 DEG C/
Minute, 800 DEG C to the crystallization temperature point finally set, heating rate is 1-3 DEG C/min, and crystallization temperature is 1130-1180 DEG C,
Heat preservation 1-3 hour, then with 2-5 DEG C/min of rate of temperature fall be cooled to 100 DEG C hereinafter, cut, polish to get.
It is 3. according to claim 2 using molybdic tailing as the preparation method of the building decorative glass ceramics of main material, feature
It also resides in and is surface-treated including glass ball particle obtained in step 3) is laid in refractory-material dies, utilize ceramics
Glaze flush coater is starched, the ceramic pigment prepared is equably sprayed to the surface of glass marble.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105417956B (en) * | 2016-01-17 | 2018-04-03 | 北京清迈华清控股(集团)有限公司 | The method that microlite is manufactured with tailings of high silicon iron |
| CN111250246B (en) * | 2020-04-02 | 2021-04-09 | 郑州大学 | Method for preparing cementing material by using tungsten-molybdenum tailings valuable mineral step separation component |
| CN112939468A (en) * | 2021-02-23 | 2021-06-11 | 伊春鹿鸣矿业有限公司 | Method for manufacturing microlite by utilizing molybdenum dressing tailings |
| CN112960907A (en) * | 2021-03-18 | 2021-06-15 | 海南海控特玻科技有限公司 | Coffee microcrystalline glass stone prepared from molybdenum tailings and preparation method thereof |
| CN113200681B (en) * | 2021-05-21 | 2022-05-27 | 西南科技大学 | Preparation method of fluorite-based glass ceramic substrate for solidifying molybdenum-containing high radioactive nuclear waste |
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| CN1733639A (en) * | 2004-08-12 | 2006-02-15 | 李章大 | Microcrystalline glass produced from molybdenum containing gangue and its method |
| CN101591144A (en) * | 2009-06-26 | 2009-12-02 | 武汉理工大学 | Slim CaO-Al 2O 3-SiO 2System glass ceramics and preparation |
| CN101734857A (en) * | 2009-12-30 | 2010-06-16 | 陕西乾盛环保建材工程有限公司 | Method for manufacturing black microcrystalline glass plates from molybdenum tailings |
| CN102515546A (en) * | 2011-12-16 | 2012-06-27 | 武汉理工大学 | Clinoenstatite microcrystalline glass prepared by talcum and process for same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4680347B2 (en) * | 1999-06-01 | 2011-05-11 | 株式会社オハラ | High rigidity glass ceramic substrate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733639A (en) * | 2004-08-12 | 2006-02-15 | 李章大 | Microcrystalline glass produced from molybdenum containing gangue and its method |
| CN101591144A (en) * | 2009-06-26 | 2009-12-02 | 武汉理工大学 | Slim CaO-Al 2O 3-SiO 2System glass ceramics and preparation |
| CN101734857A (en) * | 2009-12-30 | 2010-06-16 | 陕西乾盛环保建材工程有限公司 | Method for manufacturing black microcrystalline glass plates from molybdenum tailings |
| CN102515546A (en) * | 2011-12-16 | 2012-06-27 | 武汉理工大学 | Clinoenstatite microcrystalline glass prepared by talcum and process for same |
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