CN106587632B - A method of discarded flint glass is handled using fusion method and prepares devitrified glass - Google Patents

A method of discarded flint glass is handled using fusion method and prepares devitrified glass Download PDF

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CN106587632B
CN106587632B CN201611153792.1A CN201611153792A CN106587632B CN 106587632 B CN106587632 B CN 106587632B CN 201611153792 A CN201611153792 A CN 201611153792A CN 106587632 B CN106587632 B CN 106587632B
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glass
discarded
flint glass
flint
lead
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CN106587632A (en
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金哲男
杨洪英
吕建芳
佟琳琳
张勤
张德胜
宋言
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Northeastern University China
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Northeastern University China
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    • 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
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a kind of method for handling discarded flint glass using fusion method and preparing devitrified glass, comprising the following steps: industrial residue and discarded flint glass are crushed to 0.074-0.5mm respectively；Industrial residue, discarded flint glass, composition adjustment agent, nucleating agent and coke are uniformly mixed；By mixed material in 1400-1600oMelting 2-3 h under C obtains upper layer glass metal after isolating lower layer's lead bullion；Upper layer glass metal is successively annealed, coring, crystallization, obtains devitrified glass after cooling.Industrial residue and discarded flint glass are converted high value added product by the present invention, has been inherently eliminated the lead contamination of flint glass, and is utilized lead resource, has good environmental benefit, economic benefit and social benefit.

Description

A method of discarded flint glass is handled using fusion method and prepares devitrified glass
Technical field
The present invention relates to the processing of discarded flint glass and the preparation methods of devitrified glass, and in particular to a kind of to utilize melting Method method processing discarded flint glass and prepare devitrified glass.
Background technique
Since flint glass can effectively absorb X-ray, it is widely used in production cathode-ray tube (Cathode Ray Tube, abbreviation CRT).With the fast development of display technology, so that more and more cathode-ray tube displays are eliminated, Therefore largely discarded CRT is produced.The annual CRT learies in China are huge, while there are also largely useless CRT to pass through back door It is transported to China from developed country, the processing of discarded CRT has become one of the major issue in the processing of China's electron wastes. The leaded up to 20-25% of cone glass in CRT will generate serious danger to water source, soil and air if discarded CRT is arbitrarily placed Evil, and jeopardize the health of the mankind.Due to the special structure of cone glass, it is difficult to adopt conventional mode and recycles lead, cause The difficult status of discarded flint glass processing.
Meanwhile the country generates the industrial residues such as a large amount of flyash, magnesite slag every year, in addition to small part waste residue is made into water Mud is used as outside roadbed, and most of waste residue air storage not only occupies soil, also pollutes the environment.It is directed to work both at home and abroad Numerous studies have been carried out in the processing disposition of industry waste residue, wherein using waste residue production devitrified glass increasingly by the pass of people Note.
Devitrified glass is a kind of polycrystalline material as made from melting cold quenching then control crystallization, has many excellent property Can, performance indicator is often better than similar glass and ceramics.The devitrified glass prepared using metallurgical slag, flyash or cullet System mainly has CaO-Al2O3-SiO2(CAS)、CaO-Al2O3- Fe2O3 - SiO2 (CAFS)、MgO-Al2O3-SiO2(MAS) System, different without the devitrified glass principal crystalline phase of system, obtained material property is also different.Compared to CAS microcrystalline glass in series, MAS A variety of crystal phases of superior performance can be precipitated in microcrystalline glass in series, have the good characteristics such as high mechanical strength, thermal-shock resistance be good, heavier It wants, this kind of devitrified glass can be entirely free of alkali metal ion, to obtain excellent electrical property.In recent years, about benefit It has largely been reported with the research that flyash, metallurgical slag or discarded flint glass prepare devitrified glass, but these methods are most It is to be fixed the heavy metal lead in flint glass in the product, to reduce pollution using cured method.It not only wastes in this way Precious resources, and lead enters and still causes potentially to threaten and influence properties of product in product, limits the application of product.
Summary of the invention
In view of the problems of the existing technology, the present invention is provided a kind of handled using fusion method and discards flint glass and prepare The method of devitrified glass.The technical solution of the present invention is as follows:
The method for handling discarded flint glass using fusion method and preparing devitrified glass, comprising the following steps:
Industrial residue and discarded flint glass are crushed to 0.074-0.5mm respectively；
Industrial residue, discarded flint glass, composition adjustment agent, nucleating agent and coke are uniformly mixed, and control mixture Chemical composition according to mass percent are as follows: SiO235-45%, Al2O312-17%, MgO 14-19%, R2O 3-7%, CaO 3- 6%, Fe2O32-6%, TiO2Or ZrO24-10%, PbO 8-12%, wherein R2O indicates K2O and Na2O；
By mixed material in 1400-1600oMelting 2-3 h under C obtains upper layer glass metal after isolating lower layer's lead bullion；
Upper layer glass metal is successively annealed, coring, crystallization, obtains devitrified glass after cooling.
In the above method, the industrial residue is one of flyash, magnesite slag or two kinds.
In the above method, the discarded flint glass is the cone glass of discarded cathode-ray tube.
In the above method, the composition adjustment agent is that dolomite or both dolomite and feldspar mix.
In the above method, the nucleating agent is TiO2、ZrO2One of.
It is described to mix industrial residue, discarded flint glass, composition adjustment agent, nucleating agent and coke in the above method It is even, i.e., with industrial residue, discarded flint glass, composition adjustment agent, nucleating agent gross mass for 100%, wherein industrial residue is added Amount is 35-50%, and discarding flint glass additional amount is 30-40%, and dolomite additional amount is 5-14%, and feldspar additional amount is 0-10%, Nucleating agent additional amount is 5-10%；Coke additional amount is 1.1-1.5 times of discarded flint glass quality.
In the above method, the purity of lower layer's lead bullion is 98% or more.
In the above method, it is described upper layer glass metal is successively annealed, coring, crystallization, wherein the annealing conditions are as follows: annealing 550-650 DEG C of temperature, soaking time 2-4h；The coring condition are as follows: 5-10 DEG C of heating rate/min, nucleation temperature 700- 800oC, soaking time 1-3h；The crystallization condition are as follows: 2-5 DEG C of heating rate/min, crystallization temperature 850-1000oC, when heat preservation Between 2-3h.
In the above method, the lead tolerance of the devitrified glass is 1% hereinafter, lead recovery is 93% or more.
The principle that the present invention is acted synergistically using industrial residue and discarded flint glass are as follows: containing alkaline oxygenated in industrial residue Object (such as MgO, CaO) and amphoteric oxide (such as Al2O3, basic anhydride are shown as in acid condition), utilize these oxidations Object replaces alkaline assistant required for discarded flint glass carbon thermal reduction, reduces slag viscosity, keeps the lead of flint glass suitable Benefit restores and settles aggregation；Correspondingly, the SiO in flint glass2Quartz sand can be replaced as when preparing devitrified glass with waste residue Additive, while the Na in glass2O and K2O plays fluxing effect to waste residue.The present invention takes full advantage of thermal energy, by glass Progress synchronous with lead reduction is melted, energy consumption is greatly reduced.
Compared with existing industrial residue or flint glass prepare devitrified glass technique, beneficial effects of the present invention are as follows:
(1) simple process and low cost, it is only necessary to which primary melting is with regard to the preparation of achievable parent glass liquid and the reduction of lead, energy Play the role of energy-saving and emission-reduction and reduces energy consumption.
(2) lead in flint glass is reduced to metallic lead, has not only been inherently eliminated the lead contamination of flint glass, but also makes Lead resource is utilized, and is generated economic benefit in addition, reducing the lead tolerance in devitrified glass product and is improved properties of product.
(3) high value added product is converted by industrial residue and discarded flint glass, eliminates environmental pollution, had good Environmental benefit, economic benefit and social benefit.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
The present invention is described in further details with specific embodiment with reference to the accompanying drawing, described is to solution of the invention It releases rather than limits.
Embodiment 1
The method for handling discarded flint glass using fusion method and preparing devitrified glass, process flow chart is as shown in Figure 1, packet Include following steps:
(1) flyash, discarded flint glass, dolomite and coke are crushed to 0.2mm respectively；
(2) it is according to flyash for 100% with flyash, the gross mass for discarding flint glass, composition adjustment agent, nucleating agent 45%, flint glass 35%, dolomite 14%, nucleating agent TiO2For 6% and m (coke)/m (discarded flint glass)=1.2% Ingredient is uniformly mixed, and the chemical composition of mixture is according to mass percent are as follows: SiO2 38.1%、Al2O3 15.8%、MgO 16.9%、R2O 5.1%、CaO 4.7%、Fe2O3 3.4%、TiO25.8%, PbO 8.6%, wherein R2O indicates K2O and Na2O；
(3) by mixed material at 1500 DEG C melting 2.5h, obtain upper layer glass metal after isolating lower layer's lead bullion；
(4) upper layer glass metal is put into 600 DEG C of tube furnace insulation annealing 2h, then is placed in Si-Mo rod tube type resistance furnace, 750 DEG C are raised to the heating rate of 5 DEG C/min, heat preservation 3h carries out coring processing, then is warming up to 950 DEG C with the rate of 5 DEG C/min, It keeps the temperature 2h and carries out Crystallizing treatment, obtain devitrified glass after cooling.
The devitrified glass lead tolerance of the present embodiment is 0.47%, and lead recovery 93.5%, lead bullion purity reaches 98.8%.
Embodiment 2
The method for handling discarded flint glass using fusion method and preparing devitrified glass, process flow chart is as shown in Figure 1, packet Include following steps:
(1) flyash, discarded flint glass, dolomite and coke are crushed to 0.074mm respectively；
(2) it is according to flyash for 100% with flyash, the gross mass for discarding flint glass, composition adjustment agent, nucleating agent 35%, flint glass 40%, dolomite 12%, feldspar 5%, nucleating agent TiO2It (is discarded leaded for 8% and m (coke)/m Glass)=1.5% ingredient, it is uniformly mixed, the chemical composition of mixture is according to mass percent are as follows: SiO2 39.3%、Al2O3 15.5%、MgO 15.4%、R2O 5.5%、CaO 4.1%、Fe2O3 3.0%、TiO27.7%, PbO 9.4%, wherein R2O indicates K2O And Na2O；
(3) by mixed material at 1400 DEG C melting 3h, obtain upper layer glass metal after isolating lower layer's lead bullion；
(4) upper layer glass metal is put into 550 DEG C of tube furnace insulation annealing 3h, then is placed in Si-Mo rod tube type resistance furnace, 700 DEG C are raised to the heating rate of 10 DEG C/min, heat preservation 2h carries out coring processing, then is warming up to 900 with the rate of 5 DEG C/min DEG C, heat preservation 2h carries out Crystallizing treatment, obtains devitrified glass after cooling.
The devitrified glass lead tolerance of the present embodiment is 0.38%, and lead recovery 94.9%, lead bullion purity reaches 98.3%.
Embodiment 3
The method for handling discarded flint glass using fusion method and preparing devitrified glass, process flow chart is as shown in Figure 1, packet Include following steps:
(1) flyash, magnesite slag, discarded flint glass, dolomite and coke are crushed to 0.1mm respectively；
(2) it is pressed with flyash, magnesite slag, the gross mass for discarding flint glass, composition adjustment agent, nucleating agent for 100% It is 20% according to flyash, magnesite slag 20%, flint glass 35%, dolomite 5%, feldspar 10%, nucleating agent TiO2For 10% and m (coke)/m (discarded flint glass)=1.3% ingredient is uniformly mixed, and the chemical composition of mixture is according to quality hundred Divide ratio are as follows: SiO2 36.1%、Al2O3 15.2%、MgO 18.2%、R2O 4.1%、CaO 3.5%、Fe2O3 4.0%、TiO2 9.6%、 PbO 8.6%, wherein R2O indicates K2O and Na2O；
(3) by mixed material at 1550 DEG C melting 2h, obtain upper layer glass metal after isolating lower layer's lead bullion；
(4) upper layer glass metal is put into 600 DEG C of tube furnace insulation annealing 4h, then is placed in Si-Mo rod tube type resistance furnace, 780 DEG C are raised to the heating rate of 7 DEG C/min, heat preservation 2h carries out coring processing, then is warming up to 1000 with the rate of 3 DEG C/min DEG C, heat preservation 2h carries out Crystallizing treatment, obtains devitrified glass after cooling.
The devitrified glass lead tolerance of the present embodiment is 0.42%, and lead recovery 93.6%, lead bullion purity reaches 98.7%.
Embodiment 4
The method for handling discarded flint glass using fusion method and preparing devitrified glass, process flow chart is as shown in Figure 1, packet Include following steps:
(1) flyash, magnesite slag, discarded flint glass, dolomite and coke are crushed to 0.2mm respectively；
(2) it is pressed with flyash, magnesite slag, the gross mass for discarding flint glass, composition adjustment agent, nucleating agent for 100% It is 20% according to flyash, magnesite slag 20%, flint glass 40%, dolomite 9%, feldspar 6%, nucleating agent ZrO2It is 5%, And m (coke)/m (discarded flint glass)=1.1% ingredient, it is uniformly mixed, the chemical composition of mixture is according to mass percent Are as follows: SiO2 40.2%、Al2O3 14.1%、MgO 18.6%、R2O 5.2%、CaO 4.1%、Fe2O3 2.8%、ZrO2 4.9%、PbO 9.5%, wherein R2O indicates K2O and Na2O；
(3) by mixed material at 1500 DEG C melting 2h, obtain upper layer glass metal after isolating lower layer's lead bullion；
(4) upper layer glass metal is put into 650 DEG C of tube furnace insulation annealing 2h, then is placed in Si-Mo rod tube type resistance furnace, 800 DEG C are raised to the heating rate of 7 DEG C/min, heat preservation 2h carries out coring processing, then is warming up to 850 DEG C with the rate of 2 DEG C/min, It keeps the temperature 2h and carries out Crystallizing treatment, obtain devitrified glass after cooling.
The devitrified glass lead tolerance of the present embodiment is 0.38%, and lead recovery 94.9%, lead bullion purity reaches 98.3%.
Embodiment 5
The method for handling discarded flint glass using fusion method and preparing devitrified glass, process flow chart is as shown in Figure 1, packet Include following steps:
(1) flyash, discarded flint glass, dolomite and coke are crushed to 0.5mm respectively；
(2) it is according to flyash for 100% with flyash, the gross mass for discarding flint glass, composition adjustment agent, nucleating agent 40%, flint glass 40%, dolomite 11%, feldspar 2%, nucleating agent ZrO2It (is discarded leaded for 7% and m (coke)/m Glass)=1.5% ingredient, it is uniformly mixed, the chemical composition of mixture is according to mass percent are as follows: SiO2 40.3%、Al2O3 13.9%、MgO 18.5%、R2O 5.2%、CaO 4.2%、Fe2O3 2.8%、ZrO24.9%, PbO 9.4%, wherein R2O indicates K2O And Na2O；
(3) by mixed material at 1500 DEG C melting 3h, obtain upper layer glass metal after isolating lower layer's lead bullion；
(4) upper layer glass metal is put into 600 DEG C of tube furnace insulation annealing 3h, then is placed in Si-Mo rod tube type resistance furnace, 750 DEG C are raised to the heating rate of 10 DEG C/min, heat preservation 3h carries out coring processing, then is warming up to 1000 with the rate of 5 DEG C/min DEG C, heat preservation 3h carries out Crystallizing treatment, obtains devitrified glass after cooling.
The devitrified glass lead tolerance of the present embodiment is 0.34%, and lead recovery 95.2%, lead bullion purity reaches 98.6%.
Embodiment 6
The method for handling discarded flint glass using fusion method and preparing devitrified glass, process flow chart is as shown in Figure 1, packet Include following steps:
(1) flyash, magnesite slag, discarded flint glass, dolomite and coke are crushed to 0.5mm respectively；
(2) it is pressed with flyash, magnesite slag, the gross mass for discarding flint glass, composition adjustment agent, nucleating agent for 100% It is 25% according to flyash, magnesite slag 25%, flint glass 30%, dolomite 8%, feldspar 7%, nucleating agent TiO2It is 5%, And m (coke)/m (discarded flint glass)=1.5% ingredient, it is uniformly mixed, the chemical composition of mixture is according to mass percent Are as follows: SiO2 38.3%、Al2O3 16.4%、MgO 15.6%、R2O 5.1%、CaO 4.7%、Fe2O3 3.3%、TiO2 7.4%、PbO 8.5%, wherein R2O indicates K2O and Na2O；
(3) by mixed material at 1600 DEG C melting 2.5h, obtain upper layer glass metal after isolating lower layer's lead bullion；
(4) upper layer glass metal is put into 650 DEG C of tube furnace insulation annealing 2h, then is placed in Si-Mo rod tube type resistance furnace, 780 DEG C are raised to the heating rate of 8 DEG C/min, heat preservation 2h carries out coring processing, then is warming up to 900 DEG C with the rate of 3 DEG C/min, It keeps the temperature 2h and carries out Crystallizing treatment, obtain devitrified glass after cooling.
The devitrified glass lead tolerance of the present embodiment is 0.36%, and lead recovery 95.0%, lead bullion purity reaches 98.5%.

Claims (8)

1. the method for handling discarded flint glass using fusion method and preparing devitrified glass, it is characterised in that the following steps are included:
Industrial residue and discarded flint glass are crushed to 0.074-0.5mm respectively；
Industrial residue, discarded flint glass, composition adjustment agent, nucleating agent and coke are uniformly mixed, and control the change of mixture Composition is learned according to mass percent are as follows: SiO235-45%, Al2O312-17%, MgO 14-19%, R2O 3-7%, CaO 3- 6%, Fe2O32-6%, TiO2Or ZrO24-10%, PbO 8-12%, wherein R2O indicates K2O and Na2O, the industrial residue For one of flyash, magnesite slag or two kinds；
By mixed material at 1400-1600 DEG C melting 2-3h, obtain upper layer glass metal after isolating lower layer's lead bullion；
Upper layer glass metal is successively annealed, coring, crystallization, obtains devitrified glass after cooling.
2. the method according to claim 1 for handling discarded flint glass using fusion method and preparing devitrified glass, special Sign is that the discarded flint glass is the cone glass of discarded cathode-ray tube.
3. the method according to claim 1 for handling discarded flint glass using fusion method and preparing devitrified glass, special Sign is that the composition adjustment agent is that dolomite or both dolomite and feldspar mix.
4. the method according to claim 1 for handling discarded flint glass using fusion method and preparing devitrified glass, special Sign is that the nucleating agent is TiO2、ZrO2One of.
5. the method according to claim 1 for handling discarded flint glass using fusion method and preparing devitrified glass, special Sign be it is described industrial residue, discarded flint glass, composition adjustment agent, nucleating agent and coke are uniformly mixed, i.e., with Industry Waste Slag, discarded flint glass, composition adjustment agent, nucleating agent gross mass be 100%, wherein industrial residue additional amount is 35-50%, Discarded flint glass additional amount is 30-40%, and dolomite additional amount is 5-14%, and feldspar additional amount is 0-10%, and nucleating agent adds Entering amount is 5-10%；Coke additional amount is 1.1-1.5 times of discarded flint glass quality.
6. the method according to claim 1 for handling discarded flint glass using fusion method and preparing devitrified glass, special Sign is that the purity of lower layer's lead bullion is 98% or more.
7. the method according to claim 1 for handling discarded flint glass using fusion method and preparing devitrified glass, special Sign be it is described upper layer glass metal is successively annealed, coring, crystallization, wherein the annealing conditions are as follows: annealing temperature 550-650 DEG C, soaking time 2-4h；The coring condition are as follows: 5-10 DEG C of heating rate/min, 700-800 DEG C of nucleation temperature, soaking time 1-3h；The crystallization condition are as follows: 2-5 DEG C of heating rate/min, 850-1000 DEG C of crystallization temperature, soaking time 2-3h.
8. the method according to claim 1 for handling discarded flint glass using fusion method and preparing devitrified glass, special The lead tolerance for being the devitrified glass is levied 1% hereinafter, lead recovery is 93% or more.
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CN110643824B (en) * 2019-09-10 2021-08-03 广东利昌新材料有限公司 Method for cooperatively recovering cadmium refining alkali waste residues and lead-containing waste glass
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CN101914639A (en) * 2010-09-08 2010-12-15 北京科技大学 Method for recycling iron on line from iron-containing industrial slag and preparing glass ceramics frit
CN102503140A (en) * 2011-10-11 2012-06-20 郴州万容金属加工有限公司 Method for manufacturing microcrystalline glass utilizing smelting waste slag and CRT (Cathode Ray Tube) waste glass
CN104773958A (en) * 2015-04-01 2015-07-15 北京科技大学 Method for preparing hedenbergite glass ceramics by using lead slag

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JP2001172047A (en) * 1999-12-15 2001-06-26 Higuchi Seisakusho:Kk Artificial stone and method for producing the same and device for producing artificial stone
CN101613802A (en) * 2009-07-13 2009-12-30 中国科学院生态环境研究中心 The technology of reclaiming lead and producing environment-friendly building material by waste flint glass and support equipment
CN101914639A (en) * 2010-09-08 2010-12-15 北京科技大学 Method for recycling iron on line from iron-containing industrial slag and preparing glass ceramics frit
CN102503140A (en) * 2011-10-11 2012-06-20 郴州万容金属加工有限公司 Method for manufacturing microcrystalline glass utilizing smelting waste slag and CRT (Cathode Ray Tube) waste glass
CN104773958A (en) * 2015-04-01 2015-07-15 北京科技大学 Method for preparing hedenbergite glass ceramics by using lead slag

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