CN102199707A - Method for recycling and harmless treating of waste electronic glass - Google Patents

Method for recycling and harmless treating of waste electronic glass Download PDF

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Publication number
CN102199707A
CN102199707A CN2011101434729A CN201110143472A CN102199707A CN 102199707 A CN102199707 A CN 102199707A CN 2011101434729 A CN2011101434729 A CN 2011101434729A CN 201110143472 A CN201110143472 A CN 201110143472A CN 102199707 A CN102199707 A CN 102199707A
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smelting
slag
lead
glass
electronic glass
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王成彦
李敦钫
郜伟
揭晓武
杨永强
尹飞
陈永强
王�忠
崔成旺
李强
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Beijing General Research Institute of Mining and Metallurgy
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Beijing General Research Institute of Mining and Metallurgy
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Priority to CN2011101434729A priority Critical patent/CN102199707A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a method for recycling and harmless treating of waste electronic glass, and relates to a smelting process utilizing an existing pyrometallurgical lead smelting method to treat various lead-containing glass substances generated after discarding of televisions and computers of which cathode ray tubes are displays. The method provided by the invention is characterized by crushing discarded electronic glass, mixing and proportioning with mineral raw materials, an auxiliary agent and carbon used as a reducing agent from lead smelting process to obtain a mixed material, and spraying the mixed material with air to a flash smelting reaction furnace for flash smelting to obtain crude lead and smelting slag; and remixing the smelting slag with carbon used as a reducing agent in a depletion electric furnace for further reducing to obtain slag with lead content lower than 2%. The method provided by the invention can effectively treat lead-containing dangerous solid wastes, and has the advantages of low treatment cost, high treatment capacity and no generation of secondary pollutants; the raw materials have high adaptability; and the generated smelting slag can be effectively utilized.

Description

A kind of recycling of waste electronic glass and method for innocent treatment
Technical field
A kind of recycling of waste electronic glass and method for innocent treatment relate to a kind of melting technology of utilizing existing pyrometallurgical smelting of lead and handle the method that relates to all kinds of flint glass class materials that cathode tube produced for the televisor and the discarded back of computer of indicating meter.
Technical background
Electronic glass (CRT Glass) mainly refers to constitute colour picture tube, black and white kinescope and the back projection TV glass bulb with projection tube, and neck pipe, picture tube stem stem are with glass components such as pipe glass, eutectic solder glass powder, used in electron gun glass frosted pillars, it is the core component that constitutes cathode-ray tube display, i.e. picture tube glass.Cathode tube (Cathode Ray Tube, CRT, be commonly called as picture tube) be widely used in making the indicating meter picture tube of televisor and computer, for preventing X-radiation, electronic glass has added a large amount of lead during fabrication, according to the different size of picture tube, the lead content of each picture tube is about 0.5~4 kilogram.
CRT is divided into black and white and colored two classes, and its structure is roughly the same.The color CRT indicating meter mainly is made up of electron beam gun, deflector coil, shadow mask, functional coat and glass shell etc.Black and white CRT structure is simple relatively, compares with color CRT, does not have parts such as explosion-proof steel ring, shadow mask.The CRT that televisor and graphoscope adopted does not all have significant difference on structure and material.Color CRT glass bulb surfaces externally and internally has various functional coats, as fluorescent material etc.; The cone glass internal surface is an iron oxide layer, and outside surface is a graphite linings.In the color CRT panel glass not leaded (Pb) or to contain Pb few, PbO content is about 0~4%, but baric (Ba), (Sr) is higher for strontium; Plumbous oxide (PbO) content in pipe awl, the neck is about 15~35%; PbO content is up to more than 70~85% in the weld seam scolder, and the lead tolerance of black and white CRT is then low than color CRT glass.
Waste electronic glass mainly is meant is disassembling all kinds of category of glass materials that televisor and computer produced that depleted is indicating meter with the cathode ray tube (CRT), promptly discarded CRT electronic glass.Press CRT structure and composition and divide, CRT glass is divided into panel glass (Panel Glass), cone glass (Funnel Glass) and neck glass (Neck Glass or Tube Glass), and they are one by low-melting glass solder welding.General neck is to be welded on the pipe awl of CRT, quality seldom, composition is approaching, its fair counting in the cone glass quality.
Along with the fast development of electronic apparatus industry and the raising of social consumption level, electron wastes has become one of the fastest waste of rate of growth, and the environmental stress that is brought becomes increasingly conspicuous.Electron wastes contains multiple poisonous, objectionable impurities and metallic element, as lead, mercury, cadmium, antimony, sexavalent chrome, polychlorobiphenyl etc., belongs to persistent pollutant.After electron wastes becomes electronic waste and enters municipal wastes,, will produce serious harm, human healthy of infringement to water source, soil and air if treatment and disposal is improper.From 1997 to 2004, the U.S. only computer just had 3.15 hundred million to be eliminated, and wherein contained 550,000 tons of Pb, 900 tons of Cd, 180 tons of Hg and 500 tons of sexavalent chromes, and early stage computer mainly adopts CRT glass picture tube, and Hazardous substances content is big.Harm is big and quantity is maximum surely belongs to CRT glass in the electron wastes, according to statistics, the CRT glass quality accounts for 47.6% of televisor quality, and CRT glass accounts for 12% of electron wastes total amount that the U.S. collected, and 40% lead comes from electric equipment products in U.S.'s garbage loading embeading thing.The A2010 clauses and subclauses stipulate that clearly " cullet of cathode emission pipe and other have radioactive glass " has danger in " control Hazardous wastes transboundary movement and disposal Basel Convention thereof " annex eight, it is a kind of Hazardous wastes that discarded CRT electronic glass is determined, and limits transnational cross-border output.But because to the alternative effective processing means of CRT glass seldom, therefore the past exist huge environmental pollution risk both at home and abroad often with depleted graphoscope and televisor CRT landfill disposal.
Heavy metal leaching toxicity test utilization standard method the most widely--American National Environmental Protection Agency toxicity leaches program (Toxicity Characteristics Leaching Procedure in the world when pressing, when TCLP) detecting, leaching agent is the buffered soln that Glacial acetic acid and sodium hydroxide are formed, detected result shows that Pb and Ba have very strong leaching toxicity in the discarded CRT glass, belongs to Hazardous wastes.
CRT glass toxicity is big, and is main because it contains toxic substances such as lead, barium and antimony.Lead is not teleorganic element, no any physiology function in human body, and the ideal blood lead concentration is zero, and is plumbous all poisonous to all biologies.Lead is compared with other pollutent, residence time in environment is longer, little because of its solubleness in soil, the degree of freedom that is degraded by microorganisms is little, easily in the accumulation of table soil, in the long time, can be absorbed, enter human body, cause the chronic poisoning of blood system, neural system, Digestive tract etc. by food chain by crop.Children and fetus are the most responsive to lead, and it is the most serious to be injured.Low concentration lead will produce harm to the normal cell of human body after entering human body, the plumbous works better of disturbing neurocyte by blood, in blood, destroy the existence of protoheme and the perviousness of cerebral microvascular, particularly lead is accumulated in brain and will be caused brain development slow, unsound, finally influences people's intelligence.Because the treatment and disposal of the leaded waste of solid is improper, many Lead contamination incidents have taken place in recent years.
Along with popularizing and the rapid decline of flat-panel monitor price of DTV, flat-panel monitor has replaced most of CRT monitor market, new TV and computer sharply descend with CRT monitor quantity, discarded CRT electronic glass will correspondingly reduce as the consumption of new CRT raw materials for production, and finally can be eliminated.
From developing history, the sales volume of Chinese Personal Computer rises to 2003 9600000 from 30,000 of nineteen nineties, and the sales volume of televisor then rises to 2003 years 42290000 from 6,740,000 of nineteen nineties; According to estimates, nearly 4,000 ten thousand of the recoverable amount of computer in 2003, the televisor recoverable amount reaches 4.2 hundred million, wherein overwhelming majority's CRT monitor.China is the production and consumption big country of CRT, in the period of 2001 to 2006, the annual production of Chinese CRT televisor rises to 8,400 ten thousand from the forty-two million platform, in the same period, the year consumption of China's CRT televisor rises to 5,400 ten thousand from 3,000 ten thousand, and wherein CRT output in 2005 accounts for 90% of the whole world.Along with DTV popularize and the flat panel TV price descends, from 10 years of the year two thousand twenty will be now domestic color TV by the CRT TV to the period that flat panel TV is replaced, the learies of CRT will peak in from now on several years.The national televisor of scrapping reached 3,550 ten thousand as far back as 2003.According to conservative estimation, China is about 6,000,000 tons of the CRT of usefulness electronic glass quality, and always lead tolerance is about 500,000 tons.
In discarded CRT, panel glass and Taper Pipe glass quality sum have surpassed 85% of CRT quality.Discarded CRT separates metal cap net, deflector coil and electron beam gun and CRT glass shell by disassembling; It is tube panel and pipe awl that the CRT glass shell is further disassembled, and wherein tube panel is isolated fluorescent material and white glass after washing, and promptly panel glass is bored after washing and manage, and isolates impurity and plumbiferous glass such as Graphite Powder 99, metal oxide layer, paint, i.e. cone glass.Past disassembles at home and reclaims the area, family's small workshop mode to disassemble mode more, disassemble plumbous severe overweight in regional soil and the dust.After domestic general small business disassembled depleted CRT, discarded CRT glass was cheap, often is taken as refuse treatment.Because management difficulty is big, different with general electron wastes, electroplating sludge etc., discarded CRT electronic glass after the fragmentation is very similar to the simple glass outward appearance, in accumulating or use, be difficult to find and difference, in a single day discarded CRT electronic glass has entered fields such as glass, pottery and building, be used for the manufacturing of articles for daily use and food product pack etc., there is great potential hazard in HUMAN HEALTH.Discarded CRT electronic glass majority is leaded, can not simply be used for making pottery, building materials and Glass Containers and roadbed material etc.
At present because the singularity of discarded CRT electronic glass, reclaiming both at home and abroad discarded CRT mainly concentrates on and disassembles, cleans, shields and the separating and with the new CRT of the CRT electronic glass manufacturing after the recovery etc., further develop the preparation research of flint glass material and practical application also seldom of awl.The applied research of most of depleted CRT electronic glasses mainly concentrates on the technical feasibility of pottery, building material aspect, is used to make glass-ceramic, multicellular glass etc. as research, but also seldom notes the separation and the influence of toxic substance such as Pb, Ba in the product.Therefore, because the existence of toxic substances such as Pb, Ba, the discarded CRT electronic glass that contains Pb is except that being used as new CRT raw materials for production or making the flint glass, and other practical use is limited.Desire is eliminated the toxicity of discarded CRT electronic glass and can be accessed utilization, must handle lead element wherein earlier.
Technology and support equipment that CN101613802A openly sends out reclaiming lead and producing environment-friendly building material by waste flint glass a kind of,, application technology as the second resource insufficient present situation serious at waste and old flint glass environmental pollution, determined a kind ofly to be applicable to the vacuum carbothermal reduction technology of waste and old flint glass high added value recycling and to have optimized support equipment, in reclaiming waste and old flint glass, in the lead, make remaining glass residue in removal process, form the high-quality environment-friendly building materials by control condition.
1), sintering-blast-furnace method China is the plumbous output state of whole world maximum, has comparatively various in the world various plumbous smelting process at present, and different smelting process and characteristics thereof mainly contain:.This method duration of service is remote, technology maturation reliable, it is stable to produce, construction investment is few, the rate of recovery is high.2), basic husband's Saite method.Adaptability to raw material is strong, stove operation continous-stable, and the rate of recovery height of major metal can be handled the zinc hydrometallurgy slag, reclaims plumbous zinc, silver, indium.3), the QSL method is the oxygen-enriched bottom-blowing bath smelting.Equipment is simple, leaded higher secondary materials such as the treatment of battery of can arranging in pairs or groups paste, plumbous silver-colored slag, but operation control is strict, lead-in-dreg height (5~10%), dust rate height.4), many stoves of Ka Er lead smelting process.The many stoves of Ka Er are an inclination top-blown oxygen converter, and are similar with QSL, the processing of low-grade lead material during the many stoves of Ka Er can not adapt to.5), oxygen top blown submergence smelting process (Australia Si Maitefa, Ai Safa).Belong to smelting bath smelting process, adaptability to raw material is wide, it is simple to get the raw materials ready, operation is few etc.; But dust rate is big, energy consumption is high.6), Shuiko mountain method of smelt lead.Claim the oxygen bottom-blowing method again, but only be applicable to leaded processing greater than 47% high lead ore concentrate.7), plumbous oxygen enrichment flash smelting process.Adopt oxygen enrichment flash smelting technology, process stream adaptability is stronger; Be not only applicable to the processing of lead ore concentrate, can also handle zinc hydrometallurgy slag, wet type copper smelting slag and plumbous noble metal systems slag, the metallurgical slag that produces can be used for making high-test cement.
According to discarded CRT electronic glass composition characteristic, in conjunction with the specific requirement of different plumbous smelting processes, the present invention handles discarded CRT electronic glass on the technology of plumbous oxygen enrichment flash smelting process and equipment platform.
Summary of the invention
Purpose of the present invention is the deficiency to existing at above-mentioned prior art just, providing a kind of can make plumbiferous dangerous solid waste be effectively addressed, and processing cost is cheap, treatment capacity is big, adaptability to raw material is strong, the smelting slag of output can effectively utilize, and does not produce the method for innocent treatment of the waste electronic glass of secondary pollutant.
The objective of the invention is to be achieved through the following technical solutions.
A kind of recycling of waste electronic glass and method for innocent treatment, it is characterized in that raw mineral materials, auxiliary agent and carbonaceous reducing agent mix in fragmentation of waste electronic glass and the lead smelting process, then compound is sprayed into by air and carry out flash smelting, output lead bullion, smelting slag in the flash smelting Reaktionsofen; Smelting slag in slag cleaning furnace with the carbonaceous reducing agent remix, through further reduction, output is leaded less than 2% slag.
The recycling of a kind of waste electronic glass of the present invention and method for innocent treatment, the composition that it is characterized in that carrying out the mixture of flash smelting process comprises: Pb 30%~60%, Zn 4%~10%, SiO 28%~24%, Fe 8%~24%, CaO 4%~16%, S 12%~23%, Cu<1.5%; Fe:SiO in the mixture 2Mass ratio is 0.8~1.4:1, CaO:SiO 2Mass ratio is 0.4~0.8:1.
The recycling of a kind of waste electronic glass of the present invention and method for innocent treatment, remove the lead smelting raw mineral materials when it is characterized in that preparing burden and comprise in lead ore concentrate, zinc hydrometallurgy slag, leaded wet type copper smelting slag or the plumbous noble metal systems slag one or more, outside contained each element total mass, Fe and S add with the pyrite form in the insufficient section, Fe also adds with form of iron oxide, and CaO adds with lime or Wingdale form.
What adopt is existing flash smelting technology, and raw mineral materials comprises one or more in lead ore concentrate, zinc hydrometallurgy slag, leaded wet type copper smelting slag or the plumbous noble metal systems slag, and auxiliary agent comprises pyrite, lime or Wingdale; Behind the mix; Mixture is sprayed in the flash smelting Reaktionsofen by air, carries out flash smelting at 1100~1600 ℃, output lead bullion, smelting slag; Smelting slag in slag cleaning furnace with the carbonaceous reducing agent remix, through further reduction, output is leaded less than 2% waste, is used for the cement manufacturing.
The recycling of a kind of waste electronic glass of the present invention and method for innocent treatment, it is characterized in that the leaded mass concentration of described waste electronic glass broken material is 3%~35%, broken granularity is 0.5~4mm, and the amount of allocating into adds by 5%~40% of lead smelting raw material total mass.
The recycling of a kind of waste electronic glass of the present invention and method for innocent treatment, the amount of allocating into that it is characterized in that described carbonaceous reducing agent are 3%~8% of lead smelting raw mineral materials total mass.
The recycling of a kind of waste electronic glass of the present invention and method for innocent treatment, it is characterized in that described flash smelting slag in slag cleaning furnace with the carbonaceous reducing agent remix, the quality that adds carbonaceous reducing agent is 1%~5% of a smelting slag quality, the slag cleaning furnace temperature is controlled to be 1200~1350 ℃, through further reduction, lead, zinc in the smelting slag are further reduced, and output is leaded less than 2% waste, is used for the cement manufacturing.
The recycling of a kind of waste electronic glass of the present invention and method for innocent treatment is characterized in that described carbonaceous reducing agent is coal or coke etc.
Method of the present invention, process object are various waste electronic glass crushed aggregates.After discarded is all kinds of flint glass class materials that televisor and computer produced of indicating meter through disassembling with the cathode ray tube (CRT), through after the sorting process, remove various functional coats such as surface fluorescence powder, ferric oxide, graphite,, become the waste electronic glass crushed aggregate again through fragmentation.Treatment process of the present invention is with in the raw material lead ore concentrate in waste electronic glass and the lead smelting process, zinc hydrometallurgy slag, leaded wet type copper smelting slag or the plumbous noble metal systems slag one or more, and auxiliary agent pyrite, ferric oxide, lime or mixes such as Wingdale, carbonaceous reducing agent, process high melt in flash smelting furnace, output lead bullion, smelting slag etc., smelting slag in slag cleaning furnace with the carbonaceous reducing agent remix, through further reduction, output is leaded less than 2% waste, is used to make cement.
Compare with existing known technology, the present invention has following advantage and positively effect:
1, utilize the melting technology and the equipment of existing pyrometallurgical smelting of lead,, when refining is plumbous, handle leaded waste electronic glass simultaneously, have characteristics such as less investment, treatment capacity are big by changing Technology, with the obvious advantage.
2, technology is flexible, and processing cost is low.Because the discontinuity of leaded waste electronic glass supply, set up treatment facility separately and have the problem that management difficulty is big, maintenance cost is high, and the melting technology and the equipment of employing pyrometallurgical smelting of lead only need corresponding change technical data, can in time handle the waste electronic glass of heterogeneity.
3, processing efficiency height, the comprehensive lead that reclaims, waste electronic glass is dealt carefully with, and reduces plumbous harm to environment, and does not produce secondary pollutant, helps the final harmless treatment of hazardous solid waste, and resource is utilized effectively.
Embodiment
A kind of recycling of waste electronic glass and method for innocent treatment, specific operation process comprises
1, with in the raw material lead ore concentrate in waste electronic glass crushed aggregate and the lead smelting process, zinc hydrometallurgy slag, leaded wet type copper smelting slag or the plumbous noble metal systems slag one or more, and auxiliary agent pyrite, ferric oxide, lime or Wingdale, mixes such as carbonaceous reducing agent, obtain mixture, spray in the flash smelting Reaktionsofen by air then, carry out flash smelting at 1100~1600 ℃, output lead bullion, smelting slag; Smelting slag in slag cleaning furnace with the carbonaceous reducing agent remix, through further reduction, output is leaded less than 2% waste, is used for the cement manufacturing.
2, the leaded mass concentration of waste electronic glass crushed aggregate is 3~35%, being milled to granularity during batching is 0.5~4mm, and the amount of allocating into is by one or more 5~40% the adding of total mass in lead smelting raw material lead ore concentrate, zinc hydrometallurgy slag, leaded wet type copper smelting slag or the plumbous noble metal systems slag.
3, during melting the amount of allocating into of carbonaceous reducing agent be in lead smelting raw material lead ore concentrate, zinc hydrometallurgy slag, leaded wet type copper smelting slag or the plumbous noble metal systems slag one or more total mass 3~8%.
4, the composition of mixture is Pb30~60%, Zn4~10%, SiO during melting 28~24%, Fe8~24%, CaO4~16%, S12~23%, Cu<1.5%; Fe:SiO in the mixture 2Mass ratio is 0.8~1.4:1, CaO:SiO 2Mass ratio is 0.4~0.8:1; Contained each element total mass of during batching in lead smelting raw material lead ore concentrate, zinc hydrometallurgy slag, leaded wet type copper smelting slag or plumbous noble metal systems slag one or more, Fe and S add with the pyrite form in the insufficient section, Fe also adds with form of iron oxide, and CaO adds with lime or Wingdale form.
5, smelting slag in slag cleaning furnace with the carbonaceous reducing agent remix, the quality that adds carbonaceous reducing agent is 1~5% of a smelting slag quality, the slag cleaning furnace temperature is controlled to be 1200~1350 ℃, through further reduction, lead, zinc in the smelting slag are further reduced, output is leaded less than 2% waste, is used for the cement manufacturing.
6, carbonaceous reducing agent is coal or coke etc.
Embodiment 1
Get the waste electronic glass crushed aggregate of discarded colour television set cathode tube through disassembling, obtaining after fragmentation and the sorting, leaded mass concentration is 17.9%, granularity is 3~23 mm, regrinding with ball mill, to be broken to granularity be 1~2.5 mm, with lead ore concentrate and zinc hydrometallurgy slag burden, wherein the add-on of waste electronic glass crushed aggregate is 31.1% of lead ore concentrate and two kinds of raw material containing lead total masses of zinc hydrometallurgy slag, the hard coal that adds lead ore concentrate and two kinds of raw material containing lead total masses 4.5% of zinc hydrometallurgy slag again, the hard coal granularity is 1.5~3.5 mm, again by Fe:SiO in the final blending material 2Mass ratio is 1:1 and CaO:SiO 2Mass ratio is that 0.6:1 adds pyrite, ferric oxide and lime, and forming last mixture composition is Pb32.9%, Zn6.03%, SiO 212.1%, Fe12.1%, CaO7.26%, S16.2%, Cu0.2%, last mixture is again through being milled to less than 1mm, with air mixture is sprayed in the flash smelting Reaktionsofen then, carry out melting at 1250~1450 ℃, output lead bullion and smelting slag and some other by products are as flue dust etc.; Discharge the lead bullion product, smelting slag is sent in the slag cleaning furnace, and to add granularity by 2% of smelting slag quality be the hard coal of 1.5~3.5 mm, smelting slag reduces through further down at 1200~1300 ℃, except that the flue dust of output lead, zinc, also output is leaded less than 0.87% waste, is used to make cement.
Embodiment 2
The sub-computer cathode tube of power taking is through disassembling, the waste electronic glass crushed aggregate that obtains after fragmentation and the sorting, leaded mass concentration is 21.6%, granularity is 6~19 mm, regrinding with ball mill, to be broken to granularity be 1~2.5 mm, with lead ore concentrate, leaded wet type copper smelting slag and plumbous noble metal systems slag burden, wherein the add-on of waste electronic glass crushed aggregate is a lead ore concentrate, 8% of leaded wet type copper smelting slag and three kinds of raw material containing lead total masses of plumbous noble metal systems slag, add lead ore concentrate again, the coke of leaded wet type copper smelting slag and three kinds of raw material containing lead total masses 4.9% of plumbous noble metal systems slag, coke size is 1.5~3 mm, again by Fe:SiO in the final blending material 2Mass ratio is 1:1.05 and CaO:SiO 2Mass ratio is that 0.68:1 adds pyrite, ferric oxide and lime, and forming last mixture composition is Pb40.6%, Zn4.61%, SiO 213.5%, Fe12.86%, CaO9.18%, S17.42%, Cu0.53%, last mixture is again through being milled to less than 1mm, with air mixture is sprayed in the flash smelting Reaktionsofen then, carry out melting at 1300~1450 ℃, output lead bullion and smelting slag and some other by products are as flue dust etc.; Discharge the lead bullion product, smelting slag is sent in the slag cleaning furnace, and to add granularity by 3% of smelting slag quality be the coke of 1.5~3.5 mm, smelting slag reduces through further down at 1230~1320 ℃, except that the flue dust of output lead, zinc, also output is leaded less than 1.2% waste, can be used for making cement.
Embodiment 3
Get discarded colour television set and black and white television set cathode tube through disassembling, the mixing waste electronic glass crushed aggregate that obtains after fragmentation and the sorting, leaded mass concentration is 12.37%, granularity is 3.5~40 mm, regrinding with ball mill, to be broken to granularity be 1.5~3.0 mm, with lead ore concentrate, zinc hydrometallurgy slag and plumbous noble metal systems slag burden, wherein the add-on of waste electronic glass crushed aggregate is a lead ore concentrate, 15.5% of zinc hydrometallurgy slag and three kinds of raw material containing lead total masses of plumbous noble metal systems slag, add lead ore concentrate again, the coke of zinc hydrometallurgy slag and three kinds of raw material containing lead total masses 5.2% of plumbous noble metal systems slag, coke size is 1.5~3mm, again by Fe:SiO in the final blending material 2Mass ratio is 1:1.1 and CaO:SiO 2Mass ratio is that 0.72:1 adds pyrite, ferric oxide and lime, and forming last mixture composition is Pb45.86%, Zn5.31%, SiO 215.54%, Fe14.13%, CaO11.19%, S15.6%, Cu0.08%, last mixture is again through being milled to less than 1mm, with air mixture is sprayed in the flash smelting Reaktionsofen then, carry out melting at 1300~1450 ℃, output lead bullion and smelting slag and some other by products are as flue dust etc.; Discharge the lead bullion product, smelting slag is sent in the slag cleaning furnace, and to add granularity by 4% of smelting slag quality be the coke of 1.5~3mm, smelting slag reduces through further down at 1230~1310 ℃, except that the flue dust of output lead, zinc, also output is leaded less than 1.48% waste, is used to make cement.
Embodiment 4
Get discarded colour television set and robot calculator cathode tube through disassembling, the mixing waste electronic glass crushed aggregate that obtains after fragmentation and the sorting, leaded mass concentration is 30.12%, granularity is 3.5~40 mm, regrinding with ball mill, to be broken to granularity be 1.5~3.0 mm, with lead ore concentrate and plumbous noble metal systems slag burden, wherein the add-on of waste electronic glass crushed aggregate is 14.3% of lead ore concentrate and two kinds of raw material containing lead total masses of plumbous noble metal systems slag, the coke that adds lead ore concentrate and two kinds of raw material containing lead total masses 6% of plumbous noble metal systems slag again, coke size is 1.5~3mm, again by Fe:SiO in the final blending material 2Mass ratio is 0.87:1 and CaO:SiO 2Mass ratio is that 0.67:1 adds pyrite, ferric oxide and Wingdale, and forming last mixture composition is Pb22.86%, SiO 218.24%, Fe16.03%, CaO12.29%, S20.6%, last mixture sprays into mixture in the flash smelting Reaktionsofen with air then again through being milled to less than 1mm, carries out melting at 1300~1400 ℃, output lead bullion and smelting slag and some other by products are as flue dust etc.; Discharge the lead bullion product, smelting slag is sent in the slag cleaning furnace, and to add granularity by 1% of smelting slag quality be the coke of 1.5~3mm, smelting slag reduces through further down at 1300~1350 ℃, except that the flue dust of output lead, zinc, also output is leaded less than 1.65% waste, is used to make cement.

Claims (7)

1. the recycling of a waste electronic glass and method for innocent treatment, it is characterized in that raw mineral materials, auxiliary agent and carbonaceous reducing agent mix in fragmentation of waste electronic glass and the lead smelting process, then mix is sprayed into by air and carry out flash smelting, output lead bullion, smelting slag in the flash smelting Reaktionsofen; Smelting slag in slag cleaning furnace with the carbonaceous reducing agent remix, through further reduction, output is leaded less than 2% slag.
2. the recycling of a kind of waste electronic glass according to claim 1 and method for innocent treatment, the composition that it is characterized in that carrying out the mixture of flash smelting process comprises: Pb 30%~60%, Zn 4%~10%, SiO 28%~24%, Fe 8%~24%, CaO 4%~16%, S 12%~23%, Cu<1.5%; Fe:SiO in the mixture 2Mass ratio is 0.8~1.4:1, CaO:SiO 2Mass ratio is 0.4~0.8:1.
3. the recycling of a kind of waste electronic glass according to claim 2 and method for innocent treatment, remove the lead smelting raw mineral materials when it is characterized in that preparing burden and comprise in lead ore concentrate, zinc hydrometallurgy slag, leaded wet type copper smelting slag or the plumbous noble metal systems slag one or more, outside contained each element total mass, Fe and S add with the pyrite form in the insufficient section, Fe also adds with form of iron oxide, and CaO adds with lime or Wingdale form.
4. the recycling of a kind of waste electronic glass according to claim 2 and method for innocent treatment, it is characterized in that the leaded mass concentration of described waste electronic glass broken material is 3%~35%, broken granularity is 0.5~4mm, and the amount of allocating into adds by 5%~40% of lead smelting raw material total mass.
5. the recycling of a kind of waste electronic glass according to claim 2 and method for innocent treatment, the amount of allocating into that it is characterized in that described carbonaceous reducing agent are 3%~8% of lead smelting raw mineral materials total mass.
6. the recycling of a kind of waste electronic glass according to claim 2 and method for innocent treatment, it is characterized in that described flash smelting slag in slag cleaning furnace with the carbonaceous reducing agent remix, the quality that adds carbonaceous reducing agent is 1%~5% of a smelting slag quality, the slag cleaning furnace temperature is controlled to be 1200~1350 ℃, through further reduction, make the lead in the smelting slag further be reduced to leaded less than 2%.
7. the recycling of a kind of waste electronic glass according to claim 2 and method for innocent treatment is characterized in that described carbonaceous reducing agent is a kind of in hard coal or the coke.
CN2011101434729A 2011-05-31 2011-05-31 Method for recycling and harmless treating of waste electronic glass Pending CN102199707A (en)

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CN104145063A (en) * 2012-02-10 2014-11-12 太平洋科技有限公司 Foundation structure and structure manufacturing method
CN102925700A (en) * 2012-11-07 2013-02-13 荣杨 Method for recovering precious metal from electronic waste
CN103409636B (en) * 2013-08-19 2015-03-11 开远市龙腾冶炼厂 Comprehensive recovery method of waste CRT (Cathode Ray Tube) cone glass
CN103409636A (en) * 2013-08-19 2013-11-27 开远市龙腾冶炼厂 Comprehensive recovery method of waste CRT (Cathode Ray Tube) cone glass
CN103937983A (en) * 2014-04-16 2014-07-23 湖北金洋冶金股份有限公司 Collaborative disposal method for leaded glass of waste cathode ray tubes and lead plaster of waste storage batteries
CN103937983B (en) * 2014-04-16 2016-03-16 湖北金洋冶金股份有限公司 Useless cathode tube flint glass and used and scrapped battery lead plaster cooperative disposal method
CN105779769B (en) * 2015-01-13 2017-10-27 松下知识产权经营株式会社 The separation method and separator of lead are separated from lead glass
CN105779769A (en) * 2015-01-13 2016-07-20 松下知识产权经营株式会社 Method and device of separating lead from lead glass
CN104593609A (en) * 2015-02-06 2015-05-06 郑州振中电熔新材料有限公司 Method and device for separating lead from lead-containing waste glass
CN104593609B (en) * 2015-02-06 2016-08-24 郑州振中电熔新材料有限公司 The method and apparatus of leaded cullet separation lead
CN105112682A (en) * 2015-07-08 2015-12-02 东北大学 Non-noxious treatment method for waste electronic lead-containing glass
CN105110671A (en) * 2015-08-11 2015-12-02 安徽青地球环保科技有限公司 Method for transforming lead glass into environment-friendly concrete raw material by using natural biological material
CN108707759A (en) * 2018-05-30 2018-10-26 天津仁新玻璃材料有限公司 A method of recycling lead from flint glass
CN111705223A (en) * 2020-06-28 2020-09-25 广东省资源综合利用研究所 Method for co-processing lead glass and waste catalyst

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