CN102716896B - Method for recycling copper foils and glass fibers in discarded circuit board by means of hydro-thermal treatment - Google Patents
Method for recycling copper foils and glass fibers in discarded circuit board by means of hydro-thermal treatment Download PDFInfo
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- CN102716896B CN102716896B CN201210195730.2A CN201210195730A CN102716896B CN 102716896 B CN102716896 B CN 102716896B CN 201210195730 A CN201210195730 A CN 201210195730A CN 102716896 B CN102716896 B CN 102716896B
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- wiring board
- circuit board
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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Abstract
The invention provides a hydro-thermal treatment separation method for a circuit board to overcome the shortcomings that different components are mixed, separation is incomplete, energy consumption is high, and crushing equipment is greatly abraded in the process of mechanically treating a circuit board. The hydro-thermal treatment separation method is characterized in that epoxy resin in the treated circuit board is embrittled and loses bonding capacity, and granular or platy copper foils and wirelike glass fibers are obtained after crushing. The copper foils can be further used for recycling precious metal, the glass fibers can be used for recycling fire retardants, and then the copper foils and the glass fibers can be used as building material reinforcing materials, resin reinforcing materials, catalyst carriers and the like.
Description
Technical field
The present invention relates to the separation and recovery method of valuable resource in waste and old electric electric equipment products wiring board; belong to the solid waste process new technology in environmental protection and comprehensive utilization of resources field, be particularly suitable for resource reclaim and the recycling utilization of composition metal and nonmetallic materials.
Background technology
Printed circuit board (PCB) is the basis of electronics industry, is also the core component of various electronic product, is mainly used in being connected to each other of electronic component.It is widely used in the fields such as computer, communication apparatus, measurement and control instrument instrument, household appliances.Because of the reason such as the continuous renewal replacement of ageing equipment and electronic information technology, the whole world all can produce a large amount of discarded circuit boards every year.Owing to there is the composition that can work the mischief to environment in a large number in discarded printed wiring board, as halogen flame and lead, the heavy metal elements such as cadmium, if can not get appropriate disposal, not only can cause serious pollution to environment, and can cause the serious waste of resource.Meanwhile, also containing the resource that a large amount of plastics, glass fibre, common metal, trace element and noble metal etc. are useful in discarded circuit board, in today that natural resources disparities between supply and demand are increasingly sharpened, the recovery of useless printed wiring board has very high economy of resources.
At present, China's wiring board resource recycle method mainly comprises Mechanical Method, hydrometallurgy, pyrometallurgy etc.Mechanical treatment uses physical property difference between each component to carry out the method for sorting, and comprise the steps such as dismounting, fragmentation, sorting, the material after sorting process can obtain the regenerative raw materials such as metal, plastics, glass respectively through subsequent treatment again.It is low that this processing method has cost, simple to operate, not easily causes secondary pollution, easily realizes the advantages such as scale, but mechanical separation rate is separated not thorough by powder particle diameter with the restriction of sorting particle diameter, and separated product needs further split to purify.Hydrometallurgical technology main process comprises a series of acid and corrosivity leaches, then the methods such as precipitation, solvent extraction, absorption and ion-exchange are adopted to carry out isolation andpurification process to leachate, and then reclaim metal target component, this method choice is strong, the rate of recovery is high, but chemical reagent cost is high, and very high cost of sewage disposal need be born, be not suitable for large-scale industrial production.Pyrometallurgy utilizes metallurgical furnace high temperature to heat to peel off nonmetallic substance, and noble metal is melted in other Metal Melting materials or fused salt and is separated.The advantage of this method is the electronic waste that can process form of ownership, lower to the requirement of the physical aspect of electronic waste, but in the processing procedure of pyrometallurgy, some rare precious metals and common metal can run off along with the volatilization of organic principle and deslagging, organic matter produces toxic and harmful in burning process simultaneously, and then causes serious secondary pollution.In existing wiring board recoverying and utilizing method, the extensive resource that Mechanical Method is more suitable for wiring board is recycled, but together with Copper Foil in wiring board closely bonds with glass layer, conventional breaking method is difficult to completely by broken apart for wiring board different component, if using brittle for the epoxy resin modification as binding agent, make it to lose cementation, wiring board different component is just easy to broken apart.The present invention with printed substrate in waste and old electric electric product for object, realized the overall separation of Copper Foil and glass fibre on wiring board by hydrothermal treatment consists, establish a kind of easy and simple to handle, efficiency is high, the discarded circuit board resource recycling new method of environmental protection.
Three, summary of the invention
The present invention is directed to that the different component existed in Mechanical Method process circuit plate process popular at present mixes, is separated thoroughly, energy consumption is high, disintegrating apparatus weares and teares large shortcoming, provide a kind of wiring board hydrothermal modification to dissociate processing method.By carrying out hydrothermal treatment consists to wiring board, making wiring board epoxy resin brittle, losing cementability, thus different component is fully dissociated recovery.The product obtained after broken is the Copper Foil of graininess or sheet and pulverous glass fibre.Utilize the method not only can obtain the sheet Copper Foil of higher degree, can glass fibre be reclaimed simultaneously; Copper Foil can be further used for reclaiming noble metal, and glass fibre may be used for reclaiming fire retardant, is then used in the fields such as building materials reinforcing material, resin tooth material and catalyst carrier.
This method possesses following characteristics:
1, be different from the complete cracking of cured epoxy resin in pyrolysismethod and produce poisonous and corrosive fume in a large number, slight brittle cracking phenomenon is produced at hydrothermal condition epoxy resin, simultaneous reactions carries out in closed system, treatment temperature is low, avoid the generation of poison gas, and epoxy resin loses original toughness, make wiring board more easily broken apart.
2, Copper Foil, glass fibre and epoxy resin have different thermal expansions and mechanical thermal characteristic, utilize different material thermodynamic differences at a certain temperature, can produce different deformation, and then the layering of wiring board different material is dissociated.
3, wiring board is after modification, cured epoxy resin loses toughness and becomes brittle substance, different component is very easily broken apart, after crusher in crushing, (the broken time is short, only need different component fully to be dissociated for 20 ~ 40 seconds), products therefrom is the copper sheet of graininess or sheet and pulverous glass fibre, metal efficiently can be separated with non-metallic part by selection by winnowing or screening.
The present invention completes according to the following steps:
1, can directly use for the abandoned printed circuit board produced in production process and leftover bits; For the wiring board dismantled from waste and old electric electric equipment products, first by electric hot plate or infrared heating, discarded circuit board surface solder is heated, PCB surface electronic devices and components are removed after solder fusing.
2, the wiring board removing surface element device is placed into after in stainless steel material basket and sends in hydrothermal reaction kettle, add water in still, water surface elevation is the 20%-40% of reactor inner bag height, open heating after sealing to start to heat with temperature control system, after temperature in the kettle reaches design temperature 250 DEG C ~ 400 DEG C, start timing, be incubated 0.5 ~ 1 hour.
3, process makes kettle naturally cool to room temperature after terminating, and opens reaction kettle cover, takes out stainless steel material basket, is taken out by the wiring board after process and dries.Utilize suction pump that water in still and cracked oil are pumped to oil-water separation tank in the lump subsequently to leave standstill.After water-oil separating, Xiang Shuizhong adds the Ca (OH) with bromine equivalent in brominated flame-retardant in wiring board
2in order in and aqueous phase in HBr, the water after process can recycled for multiple times.
4, the wiring board after oven dry is transferred in impact crusher, control wheel speed is 850-1500 rev/min, the broken time is 1.0-2.5 minute, then be transferred in the twin shaft shear breaker having and roll and rub function with the hands, rotating speed controls at 600-1200 rev/min, and the broken time is 0.5-2.0 minute; After broken, metallic member is graininess or sheet, and be gathered under gravity bottom disintegrating machine, the glass fabric of epoxy resin cure is then dispersed as flocculence or Powdered, and finally utilizing selection by winnowing or screen can by efficient for different component separation and recovery.
Content of the present invention is set forth further below in conjunction with Figure of description and embodiment.
Four, accompanying drawing explanation
For understanding the present invention further, with accompanying drawing, present invention process flow process and wiring board modification disintegration performance characterization are described below.
Fig. 1 is the process chart that hydro-thermal method process discarded circuit board reclaims Copper Foil and glass fibre.
Fig. 2 is the Copper Foil that reclaims after hydrothermal treatment consists of discarded circuit board and glass fibre photo.Wherein: (a) is the raw glass fiber reclaimed, (b) is through the glass fibre after processing process, and (c) and (d) is the Copper Foil reclaimed.
Five, detailed description of the invention:
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
According to Fig. 1 flow chart, with the discarded circuit board with electronic devices and components for raw material, utilize electric hot plate or infrared heater to heat PCB surface solder, PCB surface electronic devices and components are removed after solder fusing.Discarded circuit board is placed into after in stainless steel material basket and sends in modification still, and perfusion accounts for the water of kettle inner bag height 40% in hydrothermal modification still.Then open heating to heat kettle with temperature control system, when temperature in the kettle reaches (now in still, pressure is about 5MPa) after design temperature 250 DEG C, temperature retention time is 1 hour.Make kettle naturally cool to room temperature after insulating process terminates, open aspiration pump and utilize exhaust gas purification system to purify gas with foreign flavor residual in still.The wiring board slight cracking of wiring board resin portion brittle phenomenon occurs with this understanding, bending strength loss late is 94.2%, and weight reduction rates is 10.8%, and debrominate rate is 40.7%.Finally the wiring board of modification taken out and dry, first after just broken, put into crusher in crushing, the broken time is 20 seconds, after broken, metallic member is graininess or sheet, be gathered under gravity bottom disintegrating machine, the glass fabric of epoxy resin cure is then dispersed as flocculence, covers above metallic particles.Now metal and nonmetallic degree of dissociation reach 96%, and utilize selection by winnowing by efficient for different component separation and recovery, the grade of copper and the rate of recovery are respectively 90.6% and 98.7% (Fig. 2).
Embodiment 2:
According to Fig. 1 flow chart, with the discarded circuit board with electronic devices and components for raw material, utilize electric hot plate or infrared heater to heat PCB surface solder, PCB surface electronic devices and components are removed after solder fusing.Discarded circuit board is placed in stainless steel material basket and sends into afterwards in modification still and in hydrothermal modification still, pour into the water accounting for kettle inner bag height 20%.Open atmosphere control system to inflated with nitrogen in still, then open heating and heat kettle with temperature control system, when temperature in the kettle reaches after design temperature 400 DEG C (in still, pressure is about 30MPa), temperature retention time is 0.5 hour.Make kettle naturally cool to room temperature after insulating process terminates, open aspiration pump and utilize exhaust gas purification system to purify gas with foreign flavor residual in still.Wiring board with this understanding resin portion is degradable, and bending strength loss late is 99.4%, and weight reduction rates is 30.2%, and debrominate rate is 97.8%.Finally taken out by the wiring board of modification and dry, first after cutter is just broken, putting into rotating blade crusher in crushing, the broken time is 40 seconds, and after broken, metallic member is graininess or sheet, is gathered under gravity bottom disintegrating machine.Removing epoxy resin fiberglass cloth is then broken into Powdered.Metal and nonmetallic degree of dissociation reach 100%.Finally utilizing selection by winnowing or screen can by efficient for different component separation and recovery, and the grade of copper and the rate of recovery are respectively 96.7% and 98.1% (Fig. 2).
In above-mentioned example, described discarded circuit board collection disassembles enterprise from waste and old electric electric equipment products, and its composition is Cu 19.60%, Pb 0.30%, Sn 0.17%, Al 2.34%, Zn 0.01%, Ag 0.0034%, Pd 0.0016%.The invention is not restricted to above-described embodiment, described content all can be implemented, and has good effect.
Claims (2)
1. hydrothermal treatment consists reclaims the method for Copper Foil and glass fibre in discarded circuit board, it is characterized in that comprising the following steps:
(1) send in hydrothermal reaction kettle after the wiring board after removal surface element device being placed into stainless steel material basket, add water in still, water surface elevation is the 20%-40% of reactor inner bag height, then seals;
(2) open heating and implement hydrothermal treatment consists with temperature control system, after temperature in the kettle reaches 250 DEG C ~ 400 DEG C, start timing, be incubated 0.5 ~ 1 hour;
(3) process makes kettle naturally cool to room temperature after terminating, and opens reaction kettle cover, takes out stainless steel material basket, is taken out by the wiring board after process, under 90-105 DEG C of condition, dry 1-3 hour;
(4) water in kettle and cracked oil are transferred in separator and carry out water-oil separating, Xiang Shuizhong adds Ca (OH)
2, bromine content equivalent in addition and wiring board, the water after process returns in reactor and recycles;
(5) wiring board after oven dry in (3) is transferred in disintegrating machine, after broken, metallic member is graininess or sheet, be gathered under gravity bottom disintegrating machine, the glass fabric of epoxy resin cure becomes flocculence, utilizes selection by winnowing separation and recovery.
2. the method for Copper Foil and glass fibre in discarded circuit board is reclaimed according to the hydrothermal treatment consists described in right 1, it is characterized in that: described fragmentation is two sections of fragmentations, first paragraph is transferred in impact crusher by the wiring board of embrittlement, control wheel speed is 850-1500 rev/min, and the broken time is 1.0-2.5 minute; Second segment is transferred to by the broken thing of first paragraph in the twin shaft shear breaker that has and roll and rub function with the hands, and rotating speed controls at 600-1200 rev/min, and the broken time is 0.5-2.0 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210195730.2A CN102716896B (en) | 2012-06-14 | 2012-06-14 | Method for recycling copper foils and glass fibers in discarded circuit board by means of hydro-thermal treatment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210195730.2A CN102716896B (en) | 2012-06-14 | 2012-06-14 | Method for recycling copper foils and glass fibers in discarded circuit board by means of hydro-thermal treatment |
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| CN102716896A CN102716896A (en) | 2012-10-10 |
| CN102716896B true CN102716896B (en) | 2015-05-13 |
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| CN103846273B (en) * | 2014-03-13 | 2016-08-17 | 北京神雾环境能源科技集团股份有限公司 | The method and system of process circuit plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417284A (en) * | 2008-12-09 | 2009-04-29 | 中南大学 | Recovery method of waste circuit board value resource |
| CN102218439A (en) * | 2011-01-24 | 2011-10-19 | 同济大学 | Method for pyrolysis separation of valuable components from substrates of waste printed circuit boards |
| CN102219922A (en) * | 2011-03-14 | 2011-10-19 | 广东工业大学 | Comprehensive recycling method of resin component in discarded circuit board waste |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11319774A (en) * | 1998-05-15 | 1999-11-24 | Elson Kk | Continuous decomposition of pcb and device therefor |
| JP3671023B2 (en) * | 2002-04-22 | 2005-07-13 | 三菱重工業株式会社 | Method and system for treating solid organic matter containing persistent decomposable harmful substances |
| JP2006068399A (en) * | 2004-09-03 | 2006-03-16 | Mitsubishi Heavy Ind Ltd | Apparatus and method for hydrothermal decomposition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417284A (en) * | 2008-12-09 | 2009-04-29 | 中南大学 | Recovery method of waste circuit board value resource |
| CN102218439A (en) * | 2011-01-24 | 2011-10-19 | 同济大学 | Method for pyrolysis separation of valuable components from substrates of waste printed circuit boards |
| CN102219922A (en) * | 2011-03-14 | 2011-10-19 | 广东工业大学 | Comprehensive recycling method of resin component in discarded circuit board waste |
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Granted publication date: 20150513 Termination date: 20160614 |