CN102643994A - Waste cathode-ray tube cone glass machinery activation wet-process sulphur treatment method - Google Patents
Waste cathode-ray tube cone glass machinery activation wet-process sulphur treatment method Download PDFInfo
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- CN102643994A CN102643994A CN2012101388886A CN201210138888A CN102643994A CN 102643994 A CN102643994 A CN 102643994A CN 2012101388886 A CN2012101388886 A CN 2012101388886A CN 201210138888 A CN201210138888 A CN 201210138888A CN 102643994 A CN102643994 A CN 102643994A
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Abstract
The invention relates to a waste cathode-ray tube (CRT) cone glass machinery activation wet-process sulphur treatment method, which comprises coarsely crushing waste CRT cone glass to obtain CRT cone glass particles with the grain size of 0.1-1.0mm, enabling the cone glass particles after coarse crushing to conduct mechanical activation through a high-energy ball-milling machine to obtain activated CRT cone glass powder; then enabling a certain a mount of activated CRT cone glass, elemental sulfur powder and water to be added in a high pressure reactor to conduct wet-process vulcanization reaction by heating, enabling heavy metal lead in the CRT cone glass to be converted into lead sulfide crystals; and finally conducting filtering separation on a sample after the vulcanization reaction, and conducting flotation separation on a solid mixture after filtration to obtain high grade lead sulfide and solid residues. The waste cathode-ray tube cone glass machinery activation wet-process sulphur treatment method is free of use of acid solution and aqueous alkali, is combined with a traditional vulcanization process, is strong in adaptability to industrial production, and can achieve high-efficient recovery of heavy metal lead in the CRT cone glass.
Description
Technical field
The present invention relates to the electronic waste processing technology field, be specifically related to a kind of useless cone glass of cathode ray tubes mechanical activation wet method sulfurizing treatment method.
Background technology
Hazardness is big and quantity is huge should belong to cathode ray tube (CRT) glass in the electronic waste.About 5.5 hundred million of the social recoverable amount of the existing televisor of China, wherein the overwhelming majority is the CRT televisor, the recoverable amount of computingmachine CRT monitor also surpasses 4,000 ten thousand, and a large amount of electric appliance and electronic product is to superseded peak period of scrapping.The CRT glass bulb is the important component part of indicating meter, accounts for 60% of total mass.The CRT glass bulb mainly is divided into panel glass, cone glass and neck glass.Cone glass is a kind of flint glass, and its lead tolerance is about 20%.Also have resource characteristics when the CRT cone glass has the environmental hazard characteristic, it is estimated, contain 520,000 tons of metallic leads in the CRT cone glass approximately, so the lead in the CRT cone glass that will give up carries out emphasis and trend that recycling is leaded cone glass research.
Because metal is that plumbous the tax is stored in the cone glass network structure in the CRT cone glass, has extensive chemical stability, and is bigger from wherein reclaiming the metallic lead difficulty.The plumbous process for extracting that exists at present exists many technical bottlenecks and environmental problem more, is difficult to realize industriallization.As in the pyrometallurgical smelting process, replace ore in sand form to put in the lead smelter CRT cone glass as fusing assistant, realize that metal separates with glass, but this method exists problems such as the waste residue amount is big, energy consumption is high, back-end processing expense height.It is higher that subcritical method is extracted the cost that reclaims metallic lead in the CRT cone glass, lacks the marketing prospect.There are problems such as energy consumption height, complex equipments in the high temperature reduction method, so metallic lead recovery technology technology should have that processing cost is low, operating procedure is simple and easy in the CRT cone glass, and characteristics such as metal recovery rate height.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art; The object of the present invention is to provide a kind of useless cone glass of cathode ray tubes mechanical activation wet method sulfurizing treatment method; Through the mechanical activation technology useless cone glass of cathode ray tubes is carried out pre-treatment; Change the strong stability chemical property of CRT cone glass, increase its chemical dissolution property in the aqueous solution, CRT cone glass behind the mechanical activation is combined conventional wet sulfuration and flotation technology; Thereby provide process not have soda acid uses, technological operation is simple, the industrial applications practicality is stronger technology, realize its harmless treatment to reach the high efficiente callback of metallic lead in the cone glass.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of useless cone glass of cathode ray tubes mechanical activation wet method sulfurizing treatment method comprises the steps:
Step 1, the coarse crushing of CRT cone glass: the cone glass coarse crushing that will pass through after CRT awl screen separates obtains the CRT cone glass particle that particle diameter is 0.1～1.0mm;
Step 2, mechanical activation: CRT cone glass particle after the coarse crushing is carried out ball milling obtain CRT cone glass powder;
Step 3, wet method sulfuration: with water, CRT cone glass powder and elemental sulfur powder with mass ratio (100～300): (10～30): 1 adds in the autoclave, and reaction kettle pressure is 0～12MPa, under 100～300 ℃, reacts 1～8 hour;
Step 4, solid-liquid separation: from step 3, take out reaction back sample and filter, realize its solid-liquid separation, the gained solid sample is lead sulfide and CRT cone glass solid residue, and liquid is sulphurous water solution;
Step 5 adopts the lead sulfide floatation process that plumbous oxide is separated with CRT cone glass solid residue solid sample in the step 4, and sulphurous water solution is handled through the oxidation style or the precipitator method.
Carry out coarse crushing with jaw crusher or roll crusher in the said step 1.
Ball-milling medium and glass particle ball material mass ratio are 20:1 in the said step 2, at room temperature carry out mechanical activation, mechanical ball milling rotating speed 500rpm, mechanical activation time 2h.
Said ball milling carries out in planetary ball mill.
Described ball-milling medium is zirconium white or stainless steel.
The lead sulfide floatation process comprises that the method for medicines such as adding collecting agent, flotation agent, pore forming material and suppressor factor realizes separating in the said step 5.
Method of the present invention can be converted into the lead sulfide crystal with metallic lead in the cathode ray tube (CRT) cone glass that gives up, and can reclaim through the conventional wet floatation process, and in the entire reaction course, anacidity, alkaline solution uses no secondary environmental pollution problem.The high energy ball mill that the present invention simultaneously adopts is as mechanical activation equipment, and activation efficiency height and Technology are ripe, and the CRT cone glass combines the conventional wet metallurgical technology behind the mechanical activation, is widely used, and is easy to large-scale industrial production.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is explained further details.
Embodiment 1
Useless cone glass of cathode ray tubes 4g joins in the planetary high-energy ball mill ball grinder after getting coarse crushing; Ball-milling medium (zirconium white) is 20:1 with the particles filled ratio of CRT cone glass; Mechanical ball milling rotating speed 500rpm, obtains the CRT cone glass powder of mechanical activation at 2 hours mechanical activation time.
Water, CRT cone glass powder and the elemental sulfur powder ratio with mass ratio 100:30:1 is added in the autoclave, and reaction kettle pressure is 12MPa, and solid-liquid reaction is 2 hours under 300 ℃ of mechanical stirring conditions.After treating that above-mentioned leaching reaction finishes, filter and realize the mixed solution solid-liquid separation.
Sulfuration rate through analyzing metallic lead in the CRT cone glass is 26.2%.
Embodiment 2
Useless cone glass of cathode ray tubes 4g joins in the planetary high-energy ball mill ball grinder after getting coarse crushing; Ball-milling medium (zirconium white) is 20:1 with the particles filled ratio of CRT cone glass; Mechanical ball milling rotating speed 500rpm, obtains the CRT cone glass powder of mechanical activation at 2 hours mechanical activation time.
Water, CRT cone glass powder and the elemental sulfur powder ratio with mass ratio 300:10:1 is added in the autoclave, and reaction kettle pressure is 6MPa, and solid-liquid reaction is 2 hours under 220 ℃ of mechanical stirring conditions.After treating that above-mentioned leaching reaction finishes, filter and realize the mixed solution solid-liquid separation.
Sulfuration rate through analyzing metallic lead in the CRT cone glass is 64.9%.
Embodiment 3
Useless cone glass of cathode ray tubes 4g joins in the planetary high-energy ball mill ball grinder after getting coarse crushing; Ball-milling medium (zirconium white) is 20:1 with the particles filled ratio of CRT cone glass; Mechanical ball milling rotating speed 500rpm, obtains the CRT cone glass powder of mechanical activation at 2 hours mechanical activation time.
Water, CRT cone glass powder and the elemental sulfur powder ratio with mass ratio 100:30:1 is added in the autoclave, and reaction kettle pressure is 1MPa, and solid-liquid reaction is 2 hours under 300 ℃ of mechanical stirring conditions.After treating that above-mentioned leaching reaction finishes, filter and realize the mixed solution solid-liquid separation.
Sulfuration rate through analyzing metallic lead in the CRT cone glass is 88.9%.
Embodiment 4
Useless cone glass of cathode ray tubes 4g joins in the planetary high-energy ball mill ball grinder after getting coarse crushing; Ball-milling medium (zirconium white) is 20:1 with the particles filled ratio of CRT cone glass; Mechanical ball milling rotating speed 500rpm, obtains the CRT cone glass powder of mechanical activation at 2 hours mechanical activation time.
Water, CRT cone glass powder and the elemental sulfur powder ratio with mass ratio 300:30:1 is added in the autoclave, and reaction kettle pressure is 5MPa, and solid-liquid reaction is 8 hours under 300 ℃ of mechanical stirring conditions.After treating that above-mentioned leaching reaction finishes, filter and realize the mixed solution solid-liquid separation.
Sulfuration rate through analyzing metallic lead in the CRT cone glass is 99.9%.
Claims (5)
1. a useless cone glass of cathode ray tubes mechanical activation wet method sulfurizing treatment method is characterized in that, comprises the steps:
Step 1, the coarse crushing of CRT cone glass: the cone glass coarse crushing that will pass through after CRT awl screen separates obtains the CRT cone glass particle that particle diameter is 0.1～1.0mm;
Step 2, mechanical activation: CRT cone glass particle after the coarse crushing is carried out ball milling obtain CRT cone glass powder;
Step 3, wet method sulfuration: with water, CRT cone glass powder and elemental sulfur powder with mass ratio (100～300): (10～30): 1 adds in the autoclave, and reaction kettle pressure is 0～12MPa, under 100～300 ℃, reacts 1～8 hour;
Step 4, solid-liquid separation: from step 3, take out reaction back sample and filter, realize its solid-liquid separation, the gained solid sample is lead sulfide and CRT cone glass solid residue, and liquid is sulphurous water solution;
Step 5 adopts the lead sulfide floatation process that plumbous oxide is separated with CRT cone glass solid residue solid sample in the step 4, and sulphurous water solution is handled through the oxidation style or the precipitator method.
2. useless according to claim 1 cone glass of cathode ray tubes mechanical activation wet method sulfurizing treatment method is characterized in that, carries out coarse crushing with jaw crusher or roll crusher in the said step 1.
3. useless according to claim 1 cone glass of cathode ray tubes mechanical activation wet method sulfurizing treatment method; It is characterized in that ball-milling medium and glass particle ball material mass ratio are 20:1 in the said step 2, at room temperature carry out mechanical activation; Mechanical ball milling rotating speed 500rpm, mechanical activation time 2h.
4. like claim 1 or 3 said useless cone glass of cathode ray tubes mechanical activation wet method sulfurizing treatment methods, it is characterized in that said ball milling carries out in planetary ball mill.
5. like the said useless cone glass of cathode ray tubes mechanical activation wet method sulfurizing treatment method of claim 3, it is characterized in that described ball-milling medium is zirconium white or stainless steel.
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| CN2012101388886A CN102643994A (en) | 2012-05-07 | 2012-05-07 | Waste cathode-ray tube cone glass machinery activation wet-process sulphur treatment method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925691A (en) * | 2012-09-17 | 2013-02-13 | 广东省生态环境与土壤研究所 | Method for recycling lead from lead-containing cathode-ray tube glass in discarded electronic waste |
| CN103818948A (en) * | 2014-02-17 | 2014-05-28 | 河南理工大学 | Preparation method of thermoelectric compound |
| CN104607284A (en) * | 2014-12-31 | 2015-05-13 | 上海第二工业大学 | Mechanical activation and wet vulcanization treatment method of waste cathode ray tube cone glass |
| CN108341656A (en) * | 2017-01-23 | 2018-07-31 | 广东省生态环境技术研究所 | A kind of innoxious method for preparing ceramics of cathode-ray tube glass |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824543A (en) * | 2010-05-27 | 2010-09-08 | 中南大学 | Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste |
| CN102417989A (en) * | 2011-11-24 | 2012-04-18 | 上海第二工业大学 | Method for extracting metallic lead from recovered waste lead-containing glass |
-
2012
- 2012-05-07 CN CN2012101388886A patent/CN102643994A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824543A (en) * | 2010-05-27 | 2010-09-08 | 中南大学 | Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste |
| CN102417989A (en) * | 2011-11-24 | 2012-04-18 | 上海第二工业大学 | Method for extracting metallic lead from recovered waste lead-containing glass |
Non-Patent Citations (1)
| Title |
|---|
| WENYI YUAN,ET AL.: "Innovated Application of Mechanical Activation To Separate Lead from Scrap Cathode Ray Tube Funnel Glass", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》, no. 46, 4 March 2012 (2012-03-04), pages 4109 - 4114 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925691A (en) * | 2012-09-17 | 2013-02-13 | 广东省生态环境与土壤研究所 | Method for recycling lead from lead-containing cathode-ray tube glass in discarded electronic waste |
| CN102925691B (en) * | 2012-09-17 | 2014-01-29 | 广东省生态环境与土壤研究所 | Method for recycling lead from lead-containing cathode-ray tube glass in discarded electronic waste |
| 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 |
| CN103818948A (en) * | 2014-02-17 | 2014-05-28 | 河南理工大学 | Preparation method of thermoelectric compound |
| CN103818948B (en) * | 2014-02-17 | 2015-04-15 | 河南理工大学 | Preparation method of thermoelectric compound |
| CN104607284A (en) * | 2014-12-31 | 2015-05-13 | 上海第二工业大学 | Mechanical activation and wet vulcanization treatment method of waste cathode ray tube cone glass |
| CN108341656A (en) * | 2017-01-23 | 2018-07-31 | 广东省生态环境技术研究所 | A kind of innoxious method for preparing ceramics of cathode-ray tube glass |
| CN108341656B (en) * | 2017-01-23 | 2021-07-23 | 广东省科学院生态环境与土壤研究所 | Method for preparing ceramic from cathode ray tube glass in harmless manner |
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Application publication date: 20120822 |