CN102676826A - Method for extracting lead from waste CRT (Cathode Ray Tube) cone glass - Google Patents
Method for extracting lead from waste CRT (Cathode Ray Tube) cone glass Download PDFInfo
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- CN102676826A CN102676826A CN2012101487970A CN201210148797A CN102676826A CN 102676826 A CN102676826 A CN 102676826A CN 2012101487970 A CN2012101487970 A CN 2012101487970A CN 201210148797 A CN201210148797 A CN 201210148797A CN 102676826 A CN102676826 A CN 102676826A
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Abstract
The invention relates to a method for extracting lead from waste CRT (Cathode Ray Tube) cone glass, comprising the specific steps of: (A) mechanically and roughly crushing the waste CRT cone glass and then finely crushing the waste CRT cone glass into 100-200 meshes; then mechanically milling for 4-12 hours to obtain a reaction raw material; (B) taking fluosilicic acid as an extracting agent at the temperature of 90-100 DEG C and continuously strengthening and leaching for 4-12 hours; and cooling and filtering to obtain a lead fluorosilicate solution; (C) slowly adding a pre-prepared dilute sulfuric acid solution into the lead fluorosilicate solution to form lead sulfate sediment; adjusting pH (Potential of Hydrogen) to complete precipitate; and (D) cooling and filtering; repeatedly washing a filter cake with de-ionized water for 3-5 times; and drying a white lead sulfate filter cake at 80 DEG C for 2-8 hours in vacuum to obtain a lead sulfate product with a higher purity, wherein the collected filtering solution is a regenerated fluosilicic acid solution and can be recycled and reused. The process does not generate secondary pollution; a waste liquid closed loop is realized in the whole process; and compared with a pyrogenic process lead smelting technology, the method has the advantages of low cost, simple technology and high production addition value.
Description
Technical field
The invention belongs to environmental protection technical field, be specifically related to a kind of method of from discarded CRT cone glass, extracting lead.Be applicable to the harmless treatment and the recycling of useless CRT glass.
Background technology
Along with the update of display product, increasing cathode tube (Cathode Ray Tube, be called for short CRT) televisor and the computer monitor entering waste streams that is eliminated causes the treatment and disposal of useless CRT to become the environmental problem that the whole world is paid close attention to.Through rough estimation, current global electronic rubbish (Waste Electrical and Electronic Equipment is called for short WEEE) contracts amount is about ten thousand tons of 2000-2500, and wherein learies accounts for the 20-40% of whole WEEE generation CRT product year.Televisor and computer sales data according to State Statistics Bureau announces infer that the social recoverable amount of China's televisor surpasses 400,000,000, and wherein very major part is the traditional C RT product that late 1980s gets into family.From beginning in 2003, China got into a large amount of cathode tube dates of retirement, has ten thousand CRT televisors of 2000-5000 and computer monitor to scrap every year approximately.In addition, also have every year a large amount of waste and old TVs and indicating meter to be transported to domestic from developed countries such as the U.S., Europe, Japan through back door.
The heavy metal lead that contains 20-25% in the CRT cone glass can cause very big harm to ecotope and human health if deal with improperly.Extraction and application technology to lead mainly is to lead storage battery at present, and comparatively rare about the patent and the document that extract the lead in the CRT glass.Common processing approach is the new CRT of cyclic regeneration cullet production, but along with technological progressively the eliminating of picture tube, CRT plant presses for exploitation and seeks new resource utilization method the rapid atrophy of demand of useless CRT.Producing building material products such as multicellular glass, clay brick, glass-ceramic to lead-free CRT panel glass at present is the comparatively feasible approach that utilizes.But the higher useless CRT cone glass of lead tolerance lacks feasible utilization technology for a long time.Have research to show both at home and abroad the CRT cone glass is cured or detoxifies and handle reducing the risk to environment, but they fundamentally do not solve metallic lead to environment and human harm influence, the lead in institute's conversion product is still a kind of potential harm.Therefore have only lead is extracted from discarded CRT glass and rationally utilizes the harm that could fundamentally solve heavy metal lead.
CRT cone glass staple is SiO
2-PbO-Na
2O-CaO is a glass; Lead atom wherein mainly is filled in-and O-Si-O-network body surrounds in the hole that forms, and also some lead combines with-O-Si-O-Pb-O-form, and structure is highly stable; Under normal temperature and pressure conditions, be difficult to destroy its network structure, extract metallic lead.Secondly since in the CRT glass except that containing lead, also contain a certain proportion of sodium, potassium, calcium plasma, this gives and from CRT glass, recycles heavy metal lead and bring many interference and difficulty.
What patent (publication number is 101613802A) was described is to adopt the vacuum carbothermal reduction method that glass network and structure are destroyed, and utilizes carbon reduction to go out the lead in the glass.Reaction conditions that temperature higher (temperature is 1000 ℃) that this patent needs and vacuum (system pressure is 10Pa) etc. are harsh and supporting production unit; This extraction process is complicated; Equipment condition is strict, and extraction cost is very high, thereby this technology is difficult in industry, use and promote.Chinese patent (publication number is 102051487A) utilizes highly basic under high temperature (450-800 ℃) melting condition, to destroy the glass network structure; Thereby the plumbous oxide that will dissociate out then utilizes carbon dust to reduce obtains lead; But this method energy consumption is higher; And consume a large amount of caustic soda, cause secondary pollution easily.
Summary of the invention
The object of the invention is to provide a kind of and from discarded CRT glass, extracts plumbous method,
What the present invention proposed extracts plumbous method from discarded CRT glass; To discard and carry out the mechanical ball milling activation after the CRT cone glass is milled to certain particle size, be digestion agent with the silicofluoric acid, under 90 ℃ of-100 ℃ of condition of water bath heating, stirs and leach reaction; Reaction times 4-12h; Cross and filter filter residue and filtrating, carry out precipitin reaction, get Powdered lead sulfate with pre-configured dilute sulphuric acid.Vacuum filtration can get the higher white lead sulfate product of purity after the drying.Through optimizing reaction conditions, plumbous extraction yield can reach more than 95%.
A kind of method of from discarded CRT glass, extracting lead that the present invention proposes, concrete steps are following:
(A) at first will discard the coarse breaking of CRT cone glass is big or small 1-2cm glass cullet piece, puts into the high speed disintegrator fine powder then and is broken to 100-200 order cone glass powder;
(B) cone glass powder and abrading-ball are mixed, in planetary ball mill, carry out HS and grind activation, it is 1:2-1:4 that ball milling condition is set at material ball ratio, rotating speed 380-580 rpm/min, ball milling time 4-12 h;
(C) with silicate fluoride solution as digestion agent, be reaction vessel with tool silica gel plug Erlenmeyer flask, heating in water bath 90-100 ℃, carry out lixiviate reaction under the stirring velocity 300-500 rpm/min condition;
(D) after reaction finishes, be cooled to room temperature, 45 μ m filter membrane vacuum filtrations, filter residue filtrating is separated; Filtrating with the slow precipitation titration of dilute sulphuric acid, obtains white lead sulfate deposition for water white transparency plumbous silicofluoride solution;
(E) filtering-depositing, deionized water repetitive scrubbing 3-5 time, the vacuum drying oven oven dry obtains the Powdered preferably lead sulfate product of percent crystallinity.
Among the present invention, control silicate fluoride solution concentration is 1-1.5 mol/L in the step (C), and liquid-solid ratio 5:1-10:1 is advisable, and the continuous extraction reaction times is controlled at 4-12h.
Among the present invention, drying temperature is 75-85 ℃ in the middle vacuum drying oven of step (E), and be 2-4h time of drying.
The main process basic principle of the present invention is following:
Under the high-energy ball milling condition CRT cone glass powder had the mechanical activation effect; Destroyed to a certain extent and combined fine and close-Si-O-Si-Pb-O-network in the glass; Simultaneously increase CRT cone glass powder particles specific surface area greatly, thereby improved the activity of lead in the glass.Because digestion agent silicate fluoride solution that is adopted and plumbous oxide react formed plumbous silicofluoride and have higher solubility; Simultaneously other foreign metal ion such as sodium in the glass, potassium, the isoionic silicofluoride solubility product of calcium are less; Be insoluble in water, extract plumbous selectivity so can improve silicofluoric acid.Simultaneously again because lead sulfate is a difficulty soluble salt; And the vitriol solubleness of foreign ion such as sodium, potassium that is present in the CRT cone glass is bigger; Purify so be prone to realize lead sulfate product and separate impurities, effectively avoided the higher isoionic interference of calcium, sodium, potassium of content in the glass; Used up sulfuric acid conversion is new silicofluoric acid simultaneously, and many raw materials and cost are saved in the leaching capable of circulation of regeneration silicofluoric acid.。
The present invention can effectively extract the lead in the CRT cone glass, when the minimizing heavy metal lead brings environmental pollution, can obtain the product lead sulfate.Waste liquid reusable edible in the whole process flow, the waste residue lead content is low, can not cause secondary lead to pollute to environment.So the present invention has the favorable industrial application value.
The present invention can effectively extract the lead in the discarded CRT glass, thereby alleviates the plumbous environmental hazard that is brought in the useless CRT glass greatly.Silicofluoric acid vat liquor recyclable regenerative utilizes in the technical process of the present invention; Through detecting; Lead tolerance is extremely low in the lixiviate slag, and reacted waste residue has certain chemically reactive, can fully utilize the preparation porous adsorbing material; Can not bring the advantage of secondary lead pollution, so the present invention has the favorable industrial application value to environment.
Description of drawings
Fig. 1 is the plumbous process for extracting process flow sheet of discarded CRT cone glass.
Fig. 2 is the Electronic Speculum figure of lead sulfate product.
Fig. 3 is the XRD diffractogram of lead sulfate product.
Embodiment
The object of the present invention is to provide a kind of method of from discarded CRT glass, extracting lead, following examples are intended to further specify the present invention, rather than restriction the present invention.
Embodiment 1:
The CRT cone glass appearance surface coatings of will giving up is removed clean, oven dry.After coarse breaking, fine powder are broken to 100-200 order powder, with the activation of certain material ball ratio mixing and ball milling.Ball milling condition is set at material ball ratio 1:2, and ball radius is the agate abrading-ball of 10 mm, 580 rpm/min, ball milling times 8 h.Finally can glass powder is levigate to 1-10 μ m.Cone glass powder after the activation is put into 105 ℃ of vacuum drying oven dry for standby.Through XRF analysis, its chemical constitution is following:
| Chemical constitution | Na 2O | Al 2O 3 | SiO 2 | K 2O | CaO | SrO | BaO | PbO |
| Content (wt %) | 7.38 | 3.27 | 50.8 | 8.32 | 3.89 | 0.59 | 0.65 | 21.7 |
Get cone glass powder 20.005g, 1mol/L silicofluoric acid 200ml puts into Erlenmeyer flask, and silica gel plug sealing prevents the silicate fluoride solution volatilization, heating in water bath to 90 ℃, stirring velocity 500 rpm/min, reaction times 8 h.
Reaction finishes and treats solution cooling final vacuum suction filtration; All slowly join in the above-mentioned beaker that fills leaching liquid with the dilute sulphuric acid of 0.5 mol/L, treat abundant reaction, deposition fully after; Pour solution in the beaker and deposition in vacuum filtration machine suction filtration, accomplish liquid-solid separation.
With the Powdered lead sulfate of separating 80 ℃ of dry 2-4 h in vacuum drying oven.Weigh, get lead sulfate product 5.2g.Through analyzing, its purity reaches more than 98%, and plumbous effective extraction yield is 91.2%.
Embodiment 2:
The 100-200 order cone glass powder of still getting above-mentioned reaction is some.
Ball milling condition is set at material ball ratio 1:2, and 10 mm agate abrading-balls and 3 mm agate abrading-balls are than being 1:1, rotating speed 580 rpm/min, ball milling time 12h.After ball milling finished, the cone glass powder that mill is good was put into 105 ℃ of loft drier dry for standby.
Get cone glass powder 20.008g, 1mol/l silicofluoric acid 200ml puts into Erlenmeyer flask, heating in water bath to 90 ℃, stirring velocity 500 rpm/min, reaction times 12 h.
Reaction finishes and treats solution cooling final vacuum suction filtration, and leaching liquid slowly joins in the above-mentioned beaker that fills leaching liquid with the dilute sulphuric acid of 0.5 mol/L, after treating fully to react completely, displays 1-2 hour.Solution in the beaker and deposition poured into carry out suction filtration in the vacuum filtration machine, deionized water repetitive scrubbing filter cake 3-5 time can obtain purity high product lead sulfate.
With drying in the lead sulfate vacuum drying oven, weighing must precipitate 5.4g.Through analyzing, the purity that institute obtains the product lead sulfate is more than 98%, and effective extraction yield of lead is 94.7%.
Claims (3)
1. one kind is extracted plumbous method from discarded CRT cone glass, it is characterized in that concrete steps are following:
(A) at first will discard the coarse breaking of CRT cone glass is big or small 1-2cm glass cullet piece, puts into the high speed disintegrator fine powder then and is broken to 100-200 order cone glass powder;
(B) cone glass powder and abrading-ball are mixed, in planetary ball mill, carry out HS and grind activation, it is 1:2-1:4 that ball milling condition is set at material ball ratio, rotating speed 380-580 rpm/min, ball milling time 4-12 h;
(C) with silicate fluoride solution as digestion agent, be reaction vessel with tool rubber plug Erlenmeyer flask, heating in water bath 90-100 ℃, carry out lixiviate reaction under the stirring velocity 300-500 rpm/min condition;
(D) after reaction finishes, be cooled to room temperature, 45 μ m filter membrane vacuum filtrations, filter residue filtrating is separated; Filtrating with the slow precipitation titration of dilute sulphuric acid, obtains white lead sulfate deposition for water white transparency plumbous silicofluoride solution;
(E) filtering-depositing, deionized water repetitive scrubbing 3-5 time, the vacuum drying oven oven dry obtains the Powdered preferably lead sulfate product of percent crystallinity.
2. according to claim 1 from the plumbous method of discarded CRT cone glass extraction, it is characterized in that control silicate fluoride solution concentration is 1-1.5 mol/L in the step (C), liquid-solid ratio 5:1-10:1, the continuous extraction reaction times is controlled at 4-12h.
3. according to claim 1 from the plumbous method of discarded CRT cone glass extraction, it is characterized in that drying temperature is 75-85 ℃ in the middle vacuum drying oven of step (E), be 2-4h time of drying.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101487970A CN102676826A (en) | 2012-05-15 | 2012-05-15 | Method for extracting lead from waste CRT (Cathode Ray Tube) cone glass |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150232962A1 (en) * | 2012-09-17 | 2015-08-20 | Guangdong Institute Of Eco-Environment And Soil Sciences | Method for recovering lead from lead-containing discarded electronic waste cathode ray tube 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 |
| CN106830061A (en) * | 2017-03-27 | 2017-06-13 | 河南师范大学 | A kind of recycling processing method of CRT cone glass |
| CN108217658A (en) * | 2016-12-13 | 2018-06-29 | 沁阳市昊达实业有限公司 | A kind of method using waste and old old-fashioned television picture tube production fluosilicic acid electrolyte |
| CN111705216A (en) * | 2020-06-16 | 2020-09-25 | 云南锡业股份有限公司锡业分公司 | Treatment process of tin soldering electrolytic anode mud |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101636512A (en) * | 2007-01-17 | 2010-01-27 | 米尔布鲁克铅再生科技有限公司 | From the scrap lead battery that contains electrode paste, reclaim the lead of high purity carbon lead plumbate form |
| CN101909770A (en) * | 2008-01-10 | 2010-12-08 | 学校法人芝浦工业大学 | Method of recycling useful metal |
| CN102002593A (en) * | 2010-12-01 | 2011-04-06 | 中国科学院生态环境研究中心 | Process for synthesizing nano-lead from waste cathode-ray tube (CRT) lead-containing glass by one-step method |
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2012
- 2012-05-15 CN CN2012101487970A patent/CN102676826A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101636512A (en) * | 2007-01-17 | 2010-01-27 | 米尔布鲁克铅再生科技有限公司 | From the scrap lead battery that contains electrode paste, reclaim the lead of high purity carbon lead plumbate form |
| CN101909770A (en) * | 2008-01-10 | 2010-12-08 | 学校法人芝浦工业大学 | Method of recycling useful metal |
| CN102002593A (en) * | 2010-12-01 | 2011-04-06 | 中国科学院生态环境研究中心 | Process for synthesizing nano-lead from waste cathode-ray tube (CRT) lead-containing glass by one-step method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150232962A1 (en) * | 2012-09-17 | 2015-08-20 | Guangdong Institute Of Eco-Environment And Soil Sciences | Method for recovering lead from lead-containing discarded electronic waste cathode ray tube glass |
| US9650693B2 (en) * | 2012-09-17 | 2017-05-16 | Guangdong Institute Of Eco-Environmental Science & Technology | Method for recovering lead from lead-containing discarded electronic waste cathode ray tube 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 |
| 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 |
| CN108217658A (en) * | 2016-12-13 | 2018-06-29 | 沁阳市昊达实业有限公司 | A kind of method using waste and old old-fashioned television picture tube production fluosilicic acid electrolyte |
| CN106830061A (en) * | 2017-03-27 | 2017-06-13 | 河南师范大学 | A kind of recycling processing method of CRT cone glass |
| CN111705216A (en) * | 2020-06-16 | 2020-09-25 | 云南锡业股份有限公司锡业分公司 | Treatment process of tin soldering electrolytic anode mud |
| CN111705216B (en) * | 2020-06-16 | 2021-12-03 | 云南锡业股份有限公司锡业分公司 | Treatment process of tin soldering electrolytic anode mud |
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Application publication date: 20120919 |