CN109095767A - A kind of method of vacuum heat treatment CRT cone glass removing lead oxide - Google Patents
A kind of method of vacuum heat treatment CRT cone glass removing lead oxide Download PDFInfo
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- CN109095767A CN109095767A CN201810946444.2A CN201810946444A CN109095767A CN 109095767 A CN109095767 A CN 109095767A CN 201810946444 A CN201810946444 A CN 201810946444A CN 109095767 A CN109095767 A CN 109095767A
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- cone glass
- glass
- lead
- lead oxide
- cone
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- 239000011521 glass Substances 0.000 title claims abstract description 142
- 229910000464 lead oxide Inorganic materials 0.000 title claims abstract description 55
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000010438 heat treatment Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 18
- 239000003610 charcoal Substances 0.000 claims description 11
- 238000000748 compression moulding Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000005355 lead glass Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 9
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 239000000470 constituent Substances 0.000 description 8
- 238000003801 milling Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000005331 crown glasses (windows) Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910020662 PbSiO3 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000010865 sewage 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
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
- C03C1/024—Chemical treatment of cullet or glass fibres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/06—Lead monoxide [PbO]
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
A kind of method that the present invention discloses vacuum heat treatment CRT cone glass removing lead oxide belongs to the processing of dangerous solid waste resource and recycles field.The method of the invention is to be crushed cone glass, be ground to suitable granularity first；It is then 24 hours dry in the drying box that temperature is 105 DEG C；And it is pressed and molded after evenly mixing by less than 5% mixed carbon comtent and dry cone glass, then molding cone glass piece is melted under the conditions of pressure is less than 30Pa, temperature is greater than 1200 DEG C, destroy therein-O-P-O-Si-O-reticular structure, keep the temperature 30-120min, so that lead oxide is sufficiently volatilized, and condenses in being collected in condensate pans；Finally, heat preservation terminates natural cooling, obtain glass and lead oxide condensate after de- lead respectively, lead removal efficiency up to 96.5% or more, in residue lead content be lower than 1%, it can be achieved that cone glass harmless treatment.
Description
Technical field
The present invention relates to a kind of methods of vacuum heat treatment CRT cone glass removing lead oxide, belong to dangerous solid waste resource
Processing and the field of recycling.
Background technique
Since China's TV industry develops to 21 century since 19th century the eighties, use leaded as display screen
Television set or computer there is a sharp increase in output；China has become the big producer, consumption big country and big export country of world's electric appliance.It is but close
Nian Lai, due to the rapid development of electronic technology, with the rapid emergence of China's FPD industry, a large amount of cathode-ray tube
(CRT) cone glass is eliminated, so that China enters the peak period that leaded CRT cone glass is scrapped.Show every year according to a statistics
The CRT tv product scrapped is more than 25,000,000 entablatures, arrives the year two thousand twenty, the discarded CRT cone glass quantity within the scope of entire Asia
It will be added to 1500 tons or so.A large amount of silica, lead oxide etc. are mainly contained in cone glass, wherein dioxide-containing silica is about
50% or so, the content of lead oxide about 20% or so, therefore the lead oxide in cone glass is one of important sources of lead resource.
It discards leaded CRT cone glass one and is directly subordinate to dangerous electron wastes, be that current China's electronic waste processing disposition one must solve
Certainly the problem of and important problem, the key of discarded CRT cone glass safe handling disposition are to dispose lead oxide therein processing,
If processing is mishandling, the ecological environments such as water source, soil will be generated with the harm for being difficult to estimate, and the body of the mankind can be jeopardized
Health.Currently, most countries have all forbidden carrying out cone glass landfill and burning disposal, therefore, the reasonable of CRT glass is discarded
Method of resource and approach not only become China or even in the world urgent need to solve the problem, but also lead resource in CRT cone glass
Recycle the research hotspot for having become countries in the world researcher.
Silica, lead oxide, sodium oxide molybdena, potassium oxide, aluminium oxide, calcium oxide are mainly contained in general leaded cone glass
Deng content respectively may be about 52% ~ 56%, 19% ~ 23%, 6% ~ 8%, 7.5% ~ 8.5%, 3.5% ~ 5%, 2% ~ 4%.Through forefathers' study tour
The occurrence status and crystal structure of lead in cone glass, the results showed that the lead in cone glass is with xPbO (1- x) SiO2Shape
Formula exists, and is present in cone glass system with-O-Pb-O-Si-O-reticular structure, therefore to be realized to cone glass
In the separation of lead then need energy to break this reticular structure.
In recent years, the complete process for foring the recycling of CRT glass, is broadly divided into separating technology, the cleaning procedure of CRT glass
With the recovery process of material, and it is substantially separate mature development has been obtained with cleaner technology, but it is secondary in CRT glass
The Comprehensive Recovery Technology of resource is not mature enough, and the research of the leaded cone glass of especially CRT is in the state stagnated, industrialization
Using less.
Currently, mainly having wet processing, thermal process for the processing method for recycling lead resource from discarded CRT cone glass
And combined treatment process, wherein pyrogenic attack technical study is relatively broad.Wet processing process research it is less, technique there is
The disadvantages of process flow is long, soda acid sewage is difficult and the recovery rate of lead is lower.
The method that lead oxide in the patented invention of application number 201210345035.X iron thermal reduction cone glass extracts metallic lead,
The recovery rate of its lead up to 60%, although and iron as additive to lead oxide in cone glass have good reduction effect, meeting
There is apparent change to the residue ingredient after reduction.The patent of application number 201510345361.4 passes through carbon thermal reduction cone glass
While de- lead, crown glass microballon is prepared；It is realized by the techniques such as carbon thermal reduction and the acidleach of reduzate, separation of solid and liquid
Crown glass microballon is separated with the metallic lead on its surface, while obtaining leaded leachate, and leachate passes through chemical settling or electricity
The method of solution recycles lead.The leaching rate of this lead is up to 95%, but technique is more complex, and cost may be higher, and is relatively also easy to produce water body dirt
Dye etc..Therefore seek the technique of high, at low cost, the environmentally protective processing cone glass of simple process, open pit mining rate especially
It is important.
Summary of the invention:
The purpose of the present invention is to provide a kind of methods of vacuum heat treatment CRT cone glass removing lead oxide, and this method can be efficient
Lead oxide in cone glass is removed, and the lead oxide made is enriched with, while the ingredient of its residue meets some crown glass, pottery
The component requirements of porcelain and construction material；Specifically includes the following steps:
(1) cone glass surface clean is clean, glass particle is ground into after bulk cone glass is crushed；
(2) will be spare after cone glass particle drying, by after drying cone glass particle and carbon after mixing, compression molding；
(3) cone glass of compression molding is placed in vacuum drying oven, is vacuumized, after system cold conditions pressure is less than 40Pa,
Start to be warming up to 1200 ~ 1500 DEG C with the rate of 5 ~ 30 DEG C/min, keeps the temperature 30 ~ 120min, wherein the hot pressure of system is less than
30Pa；
(4) heat preservation terminates rear furnace body cooled to room temperature, obtains lead oxide in condensation chamber, volatilization room obtains the glass after de- lead
(lead tolerance is lower than 1%).
In step (1) of the present invention bulk cone glass needs be broken into be easy to mix with carbon, molding particle, granularity 100
~300 mesh.
Carbon is 100 ~ 200 mesh charcoal powders in step (2) of the present invention, and charcoal, which is added in cone glass particle, so that them to the greatest extent may be used
The uniform mixing of energy, is pressed into certain shapes later.
The additional amount of carbon is the 0 ~ 5% of cone glass granular mass in step (2) of the present invention.
Cone glass particle and carbon are pressed into spherical, rectangular or cylindrical block after mixing in step (2) of the present invention.
The principle of the present invention: under conditions of hot pressure is lower than 30Pa, leaded CRT cone glass powder is carried out at Vacuum Heat
Science and engineering skill, mainly under high temperature and pressure PbSiO in cone glass3Reticular structure is corrupted such that lead oxide is evaporated and obtained
To enrichment, to realize basic goal of the invention；Its reaction equation is respectively as follows:
PbSiO3→PbO(s)+SiO2(s)(1)
PbO(s)→PbO(l)→PbO(g)(2)
Beneficial effects of the present invention:
(1) present invention has the characteristics that simple process, process are short, easy to operate, is conducive to the application of industrial treatment；It is heat treated
Journey is to carry out in the vacuum drying oven being completely closed, therefore avoid the spilling of lead oxide noxious material, no pollution to the environment.
(2) present invention realizes the efficient removal of lead in leaded cone glass, and removal efficiency is up to 96.5% or more, in residue
Lead content is lower than 1%, while lead oxide being made to be able to enriching and recovering；And the residue after being heat-treated can be used for preparing novel nothing
Lead glass, construction material and ceramic material etc.；Being enriched with obtained lead oxide can be used for ceramic material, radiation proof material, or even warp
It can be used for preparing lead storage battery after crossing working process；Therefore the present invention not only completes the efficient removal of lead in leaded cone glass,
And it can realize the synthetical recovery and utility value of each by-product after processing.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is that mixed carbon comtent is respectively enrichment lead oxide XRD photo under the conditions of 0%, 5% at 1400 DEG C；
Fig. 3 is that mixed carbon comtent is respectively the lead oxide scanning electron microscopic picture being enriched under the conditions of 0%, 5% at 1400 DEG C.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawings and examples.
Embodiment 1
A method of lead oxide is removed from discarded CRT cone glass by vacuum heat treatment, specifically includes the following steps:
Use leaded CRT cone glass as raw material (70g, aoxidize lead content 28.54%), it is first that cone glass surface clean is clean,
Bulk cone glass is broken into the particle for meeting milling apparatus with jaw crusher, then is worn into cone glass particle easily with grinder
In mixing, form with 100 ~ 200 mesh charcoal powders, and cone glass powder is placed in 105 DEG C of drying box it is dry for 24 hours more than；By 0%
Mixed carbon comtent and dry cone glass are molded into the condition less than 40Pa cylindric after evenly mixing, and thickness is about 3 ~ 4mm, directly
Diameter is 10mm；The cone glass of compression molding is placed in vacuum drying oven, cold conditions is then carried out and vacuumizes, when system cold conditions pressure is small
After 40Pa, starting with the rate temperature of 10 DEG C/min to 1200 DEG C, soaking time 120min, the hot pressure of system is 5 ~
10Pa。
After furnace body is cooled to room temperature, lead oxide is obtained in condensate pans, the glass after de- lead is obtained in room of volatilizing, through X-
The constituent content of ray fluorescence spectrometer analysis residue show that the removal efficiency of lead oxide is 96.59%, and the glass after taking off lead is (residual
Stay object) lead tolerance be 0.92%.
Embodiment 2
A method of lead oxide is removed from discarded CRT cone glass by vacuum heat treatment, specifically includes the following steps:
Use leaded CRT cone glass as raw material (70g, aoxidize lead content 28.54%), it is first that cone glass surface clean is clean,
Bulk cone glass is broken into the particle for meeting milling apparatus with jaw crusher, then is worn into cone glass particle easily with grinder
In mixing, form with 100 ~ 200 mesh charcoal powders, and cone glass particle is placed in 105 DEG C of drying box it is dry for 24 hours more than；And
Cubic pieces are molded into the condition less than 40Pa after evenly mixing by 0% mixed carbon comtent and dry cone glass；By compression molding
Cone glass is placed in vacuum drying oven, is then carried out cold conditions and is vacuumized, and after system cold conditions pressure is less than 40Pa, starts to start with 10
DEG C/1300 DEG C of rate Wen Zhizhi, soaking time 120min of min, the hot pressure of system is 5 ~ 10Pa.
After furnace body is cooled to room temperature, lead oxide is obtained in condensate pans, the glass after de- lead is obtained in room of volatilizing, through X-
The constituent content of ray fluorescence spectrometer analysis volatile matter and residue show that the removal efficiency of lead oxide is 97.88%, after taking off lead
Glass (residue) lead tolerance be 0.74%.
Embodiment 3
A method of lead oxide is removed from discarded CRT cone glass by vacuum heat treatment, specifically includes the following steps:
Use leaded CRT cone glass as raw material (70g, aoxidize lead content 28.54%), it is first that cone glass surface clean is clean,
Bulk cone glass is broken into the particle for meeting milling apparatus with jaw crusher, then is worn into cone glass particle easily with grinder
In mixing, form with 100 ~ 200 mesh charcoal powders, and cone glass powder is placed in 105 DEG C of drying box it is dry for 24 hours more than；And it presses
0% mixed carbon comtent and dry cone glass are pressed into the sphere of diameter 15mm after evenly mixing；The cone glass of compression molding is placed on very
In empty furnace, then carries out cold conditions and vacuumize, after system cold conditions pressure is less than 40Pa, start to start with the rate temperature of 10 DEG C/min
To 1400 DEG C, soaking time 120min, the hot pressure of system is 5 ~ 10Pa.
After furnace body is cooled to room temperature, lead oxide is obtained in condensate pans, the glass after de- lead is obtained in room of volatilizing, through X-
The constituent content of ray fluorescence spectrometer analysis volatile matter and residue show that the removal efficiency of lead oxide is 99.75%, after taking off lead
Glass (residue) lead tolerance be 0.09%.
Embodiment 4
A method of lead oxide is removed from discarded CRT cone glass by vacuum heat treatment, specifically includes the following steps:
Use leaded CRT cone glass as raw material (70g, aoxidize lead content 28.54%), it is first that cone glass surface clean is clean,
Bulk cone glass is broken into the particle for meeting milling apparatus with jaw crusher, then is worn into cone glass particle easily with grinder
In mixing, form with 100 ~ 200 mesh charcoal powders, and cone glass powder is placed in 105 DEG C of drying box it is dry for 24 hours more than；And it presses
0% mixed carbon comtent and dry cone glass are molded into the condition less than 40Pa cylindric after evenly mixing, and thickness is about 3 ~ 4mm,
Diameter is 20mm；
The cone glass of compression molding is placed in vacuum drying oven, cold conditions is then carried out and vacuumizes, when system cold conditions pressure is less than
It after 40Pa, starts to warm up, 10 DEG C/min of heating rate, is warming up to 1500 DEG C, soaking time 120min, the hot pressure of system is
5~10Pa。
After furnace body is cooled to room temperature, lead oxide is obtained in condensate pans, the glass after de- lead is obtained in room of volatilizing is penetrated through X-
The constituent content of line Fluorescence Spectrometer analysis volatile matter and residue show that the removal efficiency of lead oxide is 99.82%, after taking off lead
Glass (residue) lead tolerance is 0.04%.
Embodiment 5
A method of lead oxide is removed from discarded CRT cone glass by vacuum heat treatment, specifically includes the following steps:
Use leaded CRT cone glass as raw material (70g, aoxidize lead content 28.54%), it is first that cone glass surface clean is clean,
Bulk cone glass is broken into the particle for meeting milling apparatus with jaw crusher, then is worn into cone glass particle easily with grinder
In mixing, form with 100 ~ 200 mesh charcoal powders, and cone glass powder is placed in 105 DEG C of drying box it is dry for 24 hours more than；And it presses
1% mixed carbon comtent and dry cone glass are pressed into cylindric after evenly mixing, and thickness is about 10mm, diameter 10mm；It will be molded into
The cone glass of type is placed in vacuum drying oven, is then carried out cold conditions and is vacuumized, and after system cold conditions pressure is less than 40Pa, is started
With the rate temperature of 10 DEG C/min to 1300 DEG C, soaking time 120min, the hot pressure of system is 5 ~ 10Pa.
After furnace body is cooled to room temperature, lead oxide is obtained in condensate pans, the glass after de- lead is obtained in room of volatilizing, through X-
The constituent content of ray fluorescence spectrometer analysis volatile matter and residue show that the removal efficiency of lead oxide is 98.02%, after taking off lead
Glass (residue) lead tolerance be 0.65%.
Embodiment 6
A method of lead oxide is removed from discarded CRT cone glass by vacuum heat treatment, specifically includes the following steps:
Use leaded CRT cone glass as raw material (70g, aoxidize lead content 28.54%), it is first that cone glass surface clean is clean,
Bulk cone glass is broken into the particle for meeting milling apparatus with jaw crusher, then is worn into cone glass particle easily with grinder
In mixing, form with 100 ~ 200 mesh charcoal powders, and cone glass powder is placed in 105 DEG C of drying box it is dry for 24 hours more than；And it presses
5% mixed carbon comtent and dry cone glass are molded into the condition less than 40Pa cylindric after evenly mixing, and thickness is about 3 ~ 4mm,
Diameter is 10mm；The cone glass of compression molding is placed in vacuum drying oven, cold conditions is then carried out and vacuumizes, when system cold conditions pressure
After 40Pa, start to start with the rate temperature of 10 DEG C/min to 1300 DEG C, soaking time 120min, the hot pressure of system is
5~10Pa。
After furnace body is cooled to room temperature, lead oxide is obtained in condensate pans, the glass after de- lead is obtained in room of volatilizing, through X-
The constituent content of ray fluorescence spectrometer analysis volatile matter and residue show that the removal efficiency of lead oxide is 99.13%, after taking off lead
Glass (residue) lead tolerance be 0.15%.
Embodiment 7
A method of lead oxide is removed from discarded CRT cone glass by vacuum heat treatment, specifically includes the following steps:
Use leaded CRT cone glass as raw material (70g, aoxidize lead content 28.54%), it is first that cone glass surface clean is clean,
Bulk cone glass is broken into the particle for meeting milling apparatus with jaw crusher, then is worn into cone glass particle easily with grinder
In mixing, form with 100 ~ 200 mesh charcoal powders, and cone glass powder is placed in 105 DEG C of drying box it is dry for 24 hours more than；And it presses
5% mixed carbon comtent and dry cone glass are molded into the condition less than 40Pa cylindric after evenly mixing, and thickness is about 3 ~ 4mm,
Diameter is 10mm；The cone glass of compression molding is placed in vacuum drying oven, cold conditions is then carried out and vacuumizes, when system cold conditions pressure
After 40Pa, start to start with the rate temperature of 10 DEG C/min to 1300 DEG C, soaking time 30min, the hot pressure of system is 5
~10Pa。
After furnace body is cooled to room temperature, lead oxide is obtained in condensate pans, the glass after de- lead is obtained in room of volatilizing, through X-
The constituent content of ray fluorescence spectrometer analysis volatile matter and residue show that the removal efficiency of lead oxide is 99.45%, after taking off lead
Glass (residue) lead tolerance be 0.13%.
Embodiment 8
A method of lead oxide is removed from discarded CRT cone glass by vacuum heat treatment, specifically includes the following steps:
Use leaded CRT cone glass as raw material (70g, aoxidize lead content 28.54%), it is first that cone glass surface clean is clean,
Bulk cone glass is broken into the particle for meeting milling apparatus with jaw crusher, then is worn into cone glass particle easily with grinder
In mixing, form with 100 ~ 200 mesh charcoal powders, and cone glass powder is placed in 105 DEG C of drying box it is dry for 24 hours more than；And it presses
5% mixed carbon comtent and dry cone glass are molded into the condition less than 40Pa cylindric after evenly mixing, and thickness is about 3 ~ 4mm,
Diameter is 10mm；The cone glass of compression molding is placed in vacuum drying oven, cold conditions is then carried out and vacuumizes, when system cold conditions pressure
After 40Pa, start to start with the rate temperature of 10 DEG C/min to 1300 DEG C, soaking time 60min, the hot pressure of system is 5
~10Pa。
After furnace body is cooled to room temperature, lead oxide is obtained in condensate pans, the glass after de- lead is obtained in room of volatilizing, through X-
The constituent content of ray fluorescence spectrometer analysis volatile matter and residue show that the removal efficiency of lead oxide is 99.67%, after taking off lead
Glass (residue) lead tolerance be 0.11%.
For the effect of verifying present invention removing lead, residual glass in crucible is carried out using X-ray fluorescence analysis (XRF)
Each element content detection, testing result are as follows:
Each element content in residual glass in the different embodiments of table 1
By table 1, it can be concluded that, with the raising of heat treatment temperature and soaking time, the oxidation lead content in residual glass gradually drops
Low, when temperature is 1500 DEG C, and soaking time is 120min, the oxidation lead content in residual glass is reduced to 0.04%, and lead takes off
Except rate reaches 99.82%.
Fig. 2 is the XRD spectrum of condensate under the conditions of being unworthy of carbon at 1400 DEG C and matching carbon 5%；Show that 5% mixed carbon comtent is compared
When not matching carbon, obtained lead oxide object phase diffraction maximum is stronger.
Fig. 3 is the scanning electron microscopic picture of condensate, it can be seen that lead oxide under the conditions of being unworthy of carbon at 1400 DEG C and matching carbon 5%
Condensate is irregular crystalline particle.
Claims (5)
1. a kind of method of vacuum heat treatment CRT cone glass removing lead oxide, which is characterized in that specifically includes the following steps:
(1) cone glass surface clean is clean, glass particle is ground into after bulk cone glass is crushed；
(2) will be spare after cone glass particle drying, by after drying cone glass particle and carbon after mixing, compression molding；
(3) cone glass of compression molding is placed in vacuum drying oven, is vacuumized, after system cold conditions pressure is less than 40Pa,
Start to be warming up to 1200 ~ 1500 DEG C with the rate of 5 ~ 30 DEG C/min, keeps the temperature 30 ~ 120min, wherein the hot pressure of system is less than
30Pa；
(4) heat preservation terminates rear furnace body cooled to room temperature, obtains lead oxide in condensation chamber, volatilization room obtains the glass after de- lead
Glass.
2. the method for vacuum heat treatment CRT cone glass removing lead oxide according to claim 1, it is characterised in that: step (1)
Middle bulk cone glass needs be broken into be easy to mix with carbon, molding particle, granularity is 100~300 mesh.
3. the method for vacuum heat treatment CRT cone glass removing lead oxide according to claim 1, it is characterised in that: step (2)
Middle carbon is 100 ~ 200 mesh charcoal powders.
4. the method for vacuum heat treatment CRT cone glass removing lead oxide according to claim 1, it is characterised in that: step (2)
The additional amount of middle carbon is the 0 ~ 5% of cone glass granular mass.
5. the method for vacuum heat treatment CRT cone glass removing lead oxide according to claim 1, it is characterised in that: step (2)
Middle cone glass particle and carbon are pressed into spherical, rectangular or cylindrical block after mixing.
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| CN110316957A (en) * | 2019-07-02 | 2019-10-11 | 昆明理工大学 | A kind of method of red mud collaboration cone glass removing lead oxide |
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