CN1115210C - Method for separating metal material from waste printed circuit board and destruction distillation apparatus for processing waste materials - Google Patents
Method for separating metal material from waste printed circuit board and destruction distillation apparatus for processing waste materials Download PDFInfo
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- CN1115210C CN1115210C CN99126403A CN99126403A CN1115210C CN 1115210 C CN1115210 C CN 1115210C CN 99126403 A CN99126403 A CN 99126403A CN 99126403 A CN99126403 A CN 99126403A CN 1115210 C CN1115210 C CN 1115210C
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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
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- 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
A method for treating waste printed circuit boards, the method has the steps of: heating up for dry-distilling the waste printed circuit boards having copper foil retaining solder in at least a part of the surface, at a temperature of 250 DEG C. or higher; pulverizing the dry-distilled material of the waste printed circuit boards obtained in the heating step; and separating the pulverized material of the waste printed circuit boards obtained in the pulverizing step, into board resin component and metal component.
Description
The present invention relates to from waste printed circuit board separating metal material, as the method for Copper Foil, solder flux and electronic component, waste printed circuit board can be from used electric equipment products, or in manufacture process, produce as reclaiming in the product of inferior quality or the waste product.
The invention still further relates to and be used for heating and the metallic resin complexes of destructive distillation, and the distillation apparatus of separating metal and resin Composition.
And the present invention relates to from the refuse heating that will contain flammable organic substance and destructive distillation is carbonate with the purification techniques of the carbonizing gas of the equipment that reduces its weight.
Imbedding underground at the landfill point of control is the processing waste printed circuit board that generally adopts at present, as the method for the printed substrate in the used electric equipment products.Because control landfill point need be equipped with spacer around landfill point, avoiding harmful substance,, even when this class harmful constituent is dissolved in the rainwater, be diffused into surrounding environment as the plumbous component of the solder flux generation that keeps on the waste printed circuit board.
However, spacer may damage, and harmful substance can be diffused into environment.Therefore, still require before abandoning, to remove harmful constituent,, make them harmless as solder flux from waste printed circuit board.And because the electronic component on printed substrate and its contains precious metal such as copper, hope can be reclaimed effectively and regenerate and be used these metals.
In addition, also can produce useless printed substrate in factory, as the product of inferior quality and waste product, at present waste printed circuit board as industrial waste by top described imbed underground.Also require to reclaim effectively and precious metal that this class waste printed circuit board of regenerating is had, as copper.
Consider such situation, proposed the method that some handle waste printed circuit board.For example, a kind of method that the flat 6-228667 of Japanese Laid-Open Patent Application discloses leaves the printed substrate of electronic component and pulverizes through coarse crushing and thin comminuting method.Adopt density separation that material crushed is separated then and be recovered as two class components: the main metal-containing material of a part, as copper, another part mainly is made up of resin and filler.
To need strong crush force, because the plate of waste printed circuit board has certain toughness by the described pulverizing waste printed circuit board of this patent.Yet, when pulverizing the plate resin Composition, be enough to pulverize the excessive solder flux part of pulverizing of crush force meeting of non-printed substrate.Excessively pulverizing can make the proportion separation process that separates flux component and plate resin Composition that difficulty takes place.
Equally, electronic component is also excessively pulverized, and is difficult to separate with the plate resin Composition.Therefore, exist metal component, as solder flux and the low problem of electronic component organic efficiency always.
Disclosed the another kind of method in the prior art field of handling waste printed circuit board among the flat 8-139446 of Japanese Laid-Open Patent Application.So patent is described, can take off the electronic component that is welded on the printed substrate by applying external force onboard in heating with when melting solder flux again.
Yet in this method, external force also acts on the solder flux of heating and fusing again, makes the solder flux splash go out droplet.This has caused another difficulty that reclaims solder flux.In addition, consider that electronic component is to assemble in the circuit board with curved lead end, only is difficult to take off these electronic components from wiring board with this a kind of method.
On the other hand, many heat treatment methods be used for the regenerating product used or the contained resin material of waste product of production have been proposed.One of them method, resin material are directly as the fuel in the combustion furnace, and the heat of resin burning is as the energy.Also have a kind of method, resin material is in high-temperature low-oxygen concentration, and as heating in the blanket of nitrogen, the fuel gas of generation is as fuel.These methods are called thermal cycling method.
Another kind method with metallic resin material, comprises printed substrate and such as the metal material of connecting part, supplies with the metal molten stove.Reclaim contained precious metal, as gold, and resin material is as the substitute of reducing agent.
Use in the heat treatment method of resin material as direct fuel at those, it is pure having only the composition when the resin material of handling, and burning could be complete, and therefore, resin material could effectively utilize.And when this material contained metal, metal was stayed in the ash, needed another kind of suitable processing.
To leaving the printed substrate of a large amount of solder flux, because the high temperature that burning is handled, the solder flux of staying on the wiring board can a large amount of evaporations.Therefore, must consider the processing of emission gases.
And, be only cost-effective when using the method for metal molten stove separating metal and nonmetallic ingredient only in refuse, to contain in a large number precious metal such as gold.For example, contain the outer precious metal of copper removal in the housed device hardly, still feasible on such method and technology, but there is not economic benefit.Therefore, avoid generally adopting this method always.
And, the method that many reduction that are used to contain the refuse of flammable organic material are handled has been proposed, as the discarded rubbish of family and feed lot, the leftover bits and pieces of food processing factory.Except that burning disposal and biofermentation are handled, have by heating and destructive distillation refuse to carbonization, to reduce its method for quality.The carbide that produces can be used as the material that improves the soil.
In heating and the cracking process, essential purified treatment carbonizing gas.The prior art of relevant this method comprises with the high temperature incineration method in this gas feeding flame burner with by using oxidation catalyst oxidizes to purify the method for this gas.
In the prior art of employing incineration gases in flame burner, can use fairly simple and compact equipment.Yet the component and the quantity of the carbonizing gas that burning is produced are non-constant, and the problem of this method is to be difficult to keep completing combustion, and therefore unburned component is easy to escape.
Otherwise, in the method for use oxidation catalyst as shown in figure 19, lead to oxidation catalyst 26B from the carbonizing gas that gas retort 21A discharges through blast pipe 23B by ventilating fan 22B.By the temperature that is assemblied in the flame burner 25B maintenance oxidation catalyst 26B in the gas treatment chamber 24B.By flame oxidation, the oxidized catalyst 26B of remainder purifies the part combustible components fully near flame burner 25B.Therefore, the clean air of fully handling the back discharging discharges from Waste gas outlet 27B.
Yet in this structure, combustible concentration takes place under the situation of bigger variation from the carbonizing gas that gas retort 21B discharges, the smooth combustion meeting deterioration among the flame burner 25B.And when gas contained a large amount of inflammable substance, near the heat that produces flame burner can be excessive.It can cause the overheated problem such as oxidation catalyst 26B.
For making the flameholding among the flame burner 25B, must avoid air mixed excessive.Yet the obvious excessive meeting of inflammable substance causes the air mixture deficiency, and it can suppress the oxidation reaction on the oxidation catalyst 26B again.Therefore, unreacted matters can be escaped as smell and carbon dioxide.
And the burning among the flame burner 25B is fixed.Therefore, have only the imflammable gas to normal amount, the temperature of oxidation catalyst 26B just can remain on about 200-500 ℃.When containing salt and halide in the refuse, because 800 ℃ or higher temperature can suppress harmful substance, as the generation of dioxin (dioxins) near combustion furnace 25B.Yet oxidation catalyst 26B downstream temperature is 200-500 ℃, and dioxin is 300-700 ℃ of generation, so can produce dioxin once more.
(1) considers to handle the problems referred to above that exist in the art methods of waste printed circuit board, designed the present invention, the purpose of this invention is to provide the method for handling waste printed circuit board, this method can suppress the pollution of solder flux to the plate resin Composition of recovery, thus effective separating metal component and plate resin Composition.
The method of this processing waste printed circuit board comprises the following steps:
Under 250 ℃ or higher temperature heating with destructive distillation its at least part surface leave the waste printed circuit board of the band Copper Foil of solder flux;
The material of pulverizing after the above-mentioned waste printed circuit board destructive distillation that described heating steps obtains; With
To after the pulverizing of the described waste printed circuit board that described pulverising step obtains, separating substances be the resin Composition and the metal component of plate.
(2) the purpose of this invention is to provide from the method for waste printed circuit board separating metal component, metal component can effectively separate with waste printed circuit board in this method.
Comprise the following steps: from the method for waste printed circuit board separating metal material
Under the partially combusted atmosphere of the printed substrate of avoiding described waste printed circuit board, or under the atmosphere of avoiding described metal material oxidation, be heated to the waste printed circuit board of rare metal material, make the temperature of described at least printed wire plate portion reach 250 ℃ or higher, but be lower than 500 ℃;
Only will be ground into the sheet that is no more than pre-sizing through the basic printed wire plate portion of the described waste printed circuit board of described heating steps heating; With
According to the difference in size of described crushing piece and described metal material, be separated in the crushing piece and the metal material of staying on the described waste printed circuit board of the described basic printed wire plate portion of pulverizing in the described pulverising step.
(3) an object of the present invention is to provide from the method for waste printed circuit board separating electronic components, in this method, do not need on the solder flux of heating and fusing again, to apply external force, effectively separating electronic components and waste printed circuit board.
Comprise the following steps: from the method for waste printed circuit board separating electronic components
By the particle impact operations, predetermined particle collision is being had on the waste printed circuit board of electronic component;
In described impact operations, be connected fracture between the wiring board part that makes described waste printed circuit board and described electronic component, and do not make described wiring board partial crushing basically; With
In described impact operations, separate described electronic component from described waste printed circuit board.
(4) the present invention is in order to solve prior art problems, and purpose provides the distillation apparatus that is used to handle metallic resin, and this equipment easily can separate the resin complexes that contains inexpensive metal component.
The distillation apparatus that is used to handle the containing metal resin comprises:
The heating furnace that holds the containing metal resin,
Be used to heat described heating furnace heater and
Be used to aspirate and remove the cancellation element of the gas in the described heating furnace;
Wherein, described heater heats described heating furnace, makes the described containing metal resin that is held lose its hardness; With
Described containing metal resin is heated and does not burn, because be anoxic around described containing metal resin at least.
(5) the present invention is in order to solve prior art problems, purpose provides the distillation apparatus that is used to handle refuse, even under the situation of the quantitative changeization of the inflammable substance in the carbonizing gas that gas retort produces, still can keep stable and good burning, thereby the characteristics of the emission gases that can keep clean do not have harmful substance.
The distillation apparatus that is used to handle refuse comprises:
Be used to heat the heating furnace of input flammable debirs wherein;
Be used for heating the heater of described heating furnace at predetermined temperature;
Be used to aspirate and remove the cancellation element of the carbonizing gas that in described heating furnace, produces;
Be connected the gas treatment equipment in described discharging device upstream or downstream, this device contains oxidation catalyst;
Be connected the fuel and/or the air feeder in described gas treatment equipment upstream or downstream;
The temperature measuring equipment that is used for described oxidation catalyst; With
According to the measuring-signal of described temperature measuring equipment, the rate control device of the feeding rate of the described at least fuel supply system of control.
The carbide that main fingerboard resin part of carbide or printed wire plate portion produce in this specification, but be not limited to these.
Fig. 1 is used to implement first aspect present invention, handles the schematic diagram of the equipment of waste printed circuit board.
Fig. 2 is the embodiment according to second aspect present invention, from the flow chart of the method for waste printed circuit board separating metal material.
Fig. 3 be in the embodiment of second aspect present invention from the crushing process of the method for waste printed circuit board separating metal, the key diagram of particle impact operations.
Fig. 4 be embodiment according to second aspect present invention from the crushing process of the method for waste printed circuit board separating metal, be different from the key diagram of the particle impact operations of Fig. 3.
Fig. 5 be embodiment according to second aspect present invention from the crushing process of the method for waste printed circuit board separating metal, be different from the key diagram of the particle impact operations of Fig. 3 and Fig. 4.
Fig. 6 be embodiment according to second aspect present invention from the crushing process of the method for waste printed circuit board separating metal, the key diagram of wall impact operations.
Fig. 7 be embodiment according to second aspect present invention from the crushing process of the method for waste printed circuit board separating metal, be different from the key diagram of the wall impact operations of Fig. 6.
Fig. 8 is the embodiment according to second aspect present invention, from the crushing process of the method for waste printed circuit board separating metal, and the key diagram of metal material removal process.
Fig. 9 is according to third aspect present invention, from the key diagram of the embodiment of the method for waste printed circuit board separating electronic components.
Figure 10 is according to third aspect present invention, from the key diagram of the embodiment that is different from Fig. 9 of the method for waste printed circuit board separating electronic components.
Figure 11 is according to third aspect present invention, from the key diagram of the embodiment that is different from Fig. 9 and Figure 10 of the method for waste printed circuit board separating electronic components.
Figure 12 is the embodiment according to third aspect present invention, from the key diagram of particle separation with the method for the plate portion that is collected into small part electronic component and waste printed circuit board.
Figure 13 is first embodiment according to a forth aspect of the invention, is used to handle the structural representation of the distillation apparatus of metallic resin.
Figure 14 is second embodiment according to a forth aspect of the invention, is used to handle the structural representation of the distillation apparatus of metallic resin.
Figure 15 is the 3rd embodiment according to a forth aspect of the invention, is used to handle the structural representation of the distillation apparatus of metallic resin.
Figure 16 is first embodiment according to a fifth aspect of the invention, is used to handle the structural representation of the distillation apparatus of metallic resin.
Figure 17 is the key diagram of the operating characteristic of the said equipment.
Figure 18 is second embodiment according to a fifth aspect of the invention, is used to handle the structural representation of the distillation apparatus of refuse.
Figure 19 is the schematic diagram that is used for the characteristic of the equipment that the refuse destructive distillation handles.
[explanation of Ref. No.]
1C: heating steps
2C: pulverising step
3C: separating step
1: container
2: particle
3: waste printed circuit board
4: the arrow of the indication direction of motion
5: injection apparatus
6: shovel board
7: rotating disk
8: wall surface
9: conveyer belt
10: the collecting part of the easy metal material that descends
11: the collecting part of the difficult metal material that descends
60: electronic component
70: conveyor type
80: the particle collecting part
90: the collecting part of wiring board and electronic component mixture
100: plate portion
1A: heating furnace
2A: electric heater
3A: thermocouple
4A: temperature controller
5A: support
6A: handle material
7A: door
8A: nitrogen tube
9A: injection orifice
10A: control valve
11A: Pressure gauge
12A: exhaust duct
13A: ventilating fan
14A: delivery pipe
15A: gas treatment jar
16A: conveyer
17Aa: import
17Ab: outlet
18A: suppress the gaseous diffusion wall
19Aa, 19Ab: flexible sheets
20A: grating roller (shredding roll)
21A: cooling water pipe
22A: collect basket
1B: heating furnace
2B: electric heater
3B: furnace temperature transducer
4B: Furnace Temperature Controller
5B: conveyer belt
6B: roller member
7B: delivery pipe
8B: air inlet pipe
9B: gas purification parts
10B: blast pipe
11B: ventilating fan
12B: air outlet
13B: oxidation catalyst
14B: heat-exchanging part
15B: cartridge
16B: fuel control valve
17B: catalyst-temperature pickup
18B: combustion controller
19B: air supply pipe
Preferable embodiment of the present invention
(1) embodiment of first aspect present invention is described below
First aspect present invention comprises the heating steps of printed substrate destructive distillation under 250 ℃ or higher temperature; The pulverising step of the material of printed substrate after the heating steps destructive distillation but solder flux is not cut into particulate; The comminution of material of the waste printed circuit board that obtains at pulverising step is separated into the separating step of plate resin and metal component.
Fig. 1 is the schematic diagram that carries out from the equipment that is heated to separating step.Wherein, 1C is the heating steps that carries out on the area of heating surface, and 2C is the pulverising step that carries out with pulverizer, and 3C is the separating step that carries out with sieve.By step 1C, 2C and 3C, waste printed circuit board is separated into plate resin and metal component.
Electronic component generally is by assembling on the Copper Foil that is welded on printed substrate.The present invention pays special attention to the performance of copper contact solder flux.Because copper at high temperature can be dissolved in the solder flux very soon, the printed substrate that destructive distillation leaves solder flux can make between solder flux and the Copper Foil more firmly bonding, thereby the shake that reduces solder flux goes out (bump).Therefore, solder flux becomes and is difficult to pulverize at pulverising step, and behind pulverising step, still stays on the sheet of Copper Foil, and is the comminution of material of larger particles.
In the present embodiment, need 250 ℃ or the higher next bonding force of solder flux that in a few hours or shorter time, improve of temperature to Copper Foil.Simultaneously, the plate resin Composition becomes fragility through the destructive distillation of 250 ℃ or higher temperature, is easy to pulverize very carefully at pulverising step.Like this, metal component just becomes bigger particle as electronic component, Copper Foil and solder flux, and such metal component can separate with the plate resin Composition of pulverizing very carefully easily by the lock out operation in the separating step.Solder flux is bonded on the copper sheet and reclaims as metal component, and therefore can suppress solder flux pollutes the plate resin Composition.
Generally, the brittle resin material is easy to be crushed to approximately less than 100 microns.Therefore, when having avoided solder flux to be crushed to less than about 100 microns in the pulverising step, the lock out operation in the separating step becomes and is more prone to.
Expection embodiment of the present invention can be used for printed substrate, and wherein, the plate resin Composition is epoxy resin, phenol resin, polyester or polyimides; The base material of printed substrate is paper, glass cloth, non-woven glass fabric or nonwoven aromatic polyamides (aramid) fabric; Electronic component be by welding assembly on printed substrate.Particularly, to using paper or the aromatic polyamide resin fabric printed substrate as base material, base material has also stood thermal decomposition and has become fragility in the destructive distillation operation of heating steps, and therefore, the crushing operation in the pulverising step becomes easier.This method also can be applicable to so-called unleaded solder and common tin/lead alloy solder flux.
In the heating steps of the present invention, pyrolysis temperature is high more, and required processing time of heating steps is short more because copper is easier to be dissolved in the solder flux under higher temperature, and the shorter time bonding force between solder flux and the copper is improved.
The method of heating comprises common heater means, as electric furnace, infrared heater, far-infrared heater, induction heater and hot air gun.Destructive distillation should be carried out in vacuum and oxygen-lean atmosphere, to avoid the burning of plate resin Composition, suppresses the oxidation of metal component.Oxygen-lean atmosphere refers to that oxygen concentration is 10% or lower atmosphere, comprises inert gas.Inert gas comprises rare gas (as helium and argon), nitrogen, carbon dioxide.Nitrogen because it handles convenient by preferably as inert gas.
Under such atmosphere, generally can suppress the oxidation of metal component.Yet, when thermal decomposition material oxidation that metal component is still produced by the plate resin Composition, can suppress this class oxidation as hydrogen by in atmosphere, adding reducibility gas.
When waste printed circuit board contains fire retardant, even can not burn, so heating steps can carry out in air owing to the printed substrate component heats also in air.
In the pulverising step of the present invention, because the plate resin Composition becomes fragility in the destructive distillation of heating steps operation, even moderate crushing operation just can pulverize the plate resin Composition, and resin Composition also can be assembled with metal component more.To crushing operation, the operating condition of taking should make the solder flux surface not be worn during pulverizing.Thicker pulverizer comprises jaw crusher, gyratory milling (gyrate crusher), cone crusher, the broken machine of roller (pressure), impact grinder and hammer crusher.Thin pulverizer comprises from pulverising mill (self-pulverizingmill), ball mill, vibration milling (vibration mill) and roll mill.Other preferably method comprise: with gases at high pressure, spray to the method for wiring board as air; Wiring board is applied vibration and the method for pulverizing wiring board.The reason that these methods can be used to implement this embodiment preferably is can not wear and tear in the solder flux surface.Particularly ball milling is better, because the processing time of its simple structure and pulverizing plate resin Composition is shorter.And case hardness is suitable as abrading-ball or crushing medium less than the particle of solder flux very much, to suppress the wearing and tearing on solder flux surface.In this case, Vicker-hardness can be used as the tolerance of the hardness of crushing medium.Hardness can be coated on the surface less than the resin or the rubber of solder flux.Easy to process for making in the pulverising step, the printed substrate after the destructive distillation can be crushed to several centimetres of sizes with the short pulverizing time in advance with thick pulverizer, further then crushing resin plate portion.
In the separating step of the present invention, the plate resin Composition is ground into thin powder, and the metal component that contains solder flux do not pulverize so carefully, but is ground into bigger particle.Therefore, the screening operation by routine just can effectively separate.Separate by proportion, as centrifugal, inertia and gravity classification, they also can be separated into metal component and plate resin Composition effectively.
The present invention also comprises essential additional step except that comprising above-mentioned heating, pulverizing and separating step.In the method for an example, can allow and pass through between cutting edge slave plate and the electronic component, cut off the lead-in wire of electronic component, before heating steps, take off electronic component.In the method for another example, the solder flux with brush is removed heating and melted applies vibration, then to remove electronic component on printed substrate.
Embodiment
Printed substrate is estimated, and electronic component wherein is to be contained on the paper phenol plate of copper foil circuit figure of printing by welding.Measured the solder flux weight that is used to weld in advance.In the heating steps, assembled the printed substrate of electronic component and put into ceramic boiler tube, the pipe diameter is 90 millimeters, long 1000 millimeters.Come heated sample by external heat, and kept 120 minutes at predetermined pyrolysis temperature.After naturally cooling to 40 ℃, in managing, take out printed substrate, finished heating steps this moment.During the heating steps, in pipe, feed nitrogen with 3 liters/minute flows.
In the pulverising step, by freely falling the precomminution wiring board.Then, respectively be the ball milling that 10 millimeters ball carried out 30 minutes with diameter.
In the separating step, the comminution of material that pulverising step obtained is with 500 microns
2The sieve of perforate sieves, and is separated into the plate resin Composition that screens and stays electronic component and metal component on the sieve.In order quantitatively to determine to pollute the solder flux quantity of the plate resin Composition that is obtained, solder flux is dissolved in the acid also analyzes with the ICP emission spectrum.The solder flux pollution rate is defined as solder flux contaminant capacity and the ratio of staying the solder flux total amount on the wiring board before.
Carry out embodiment 1-3 and comparative example 1 by the different pyrolysis temperatures shown in the table 1. Embodiment 1 and 2 pulverising step use the steel ball that is coated with nylon resin.What use at the pulverising step of embodiment 3 on the other hand, is alumina balls.
Table 1
| Pyrolysis temperature (℃) | Solder flux pollution rate (%) | |
| | 250 | 0.5 |
| | 600 | 0.4 |
| | 250 | 4.5 |
| Comparative example 1 | 230 | Do not pulverize plate |
Among the embodiment 1,2 and 3, pyrolysis temperature is higher, owing to the shake that has reduced solder flux by the enough bonding forces between heating steps copper and the solder flux goes out.The result of this situation is that the solder flux pollution rate on the plate resin Composition that subsequently separating step obtains is lower.In contrast, in the comparative example 1, pyrolysis temperature is not high enough in the heating steps, causes the plate resin Composition not have enough fragility, and wiring board just can not fully be pulverized at pulverising step.Therefore, the plate resin Composition can not separate with metal material with electronic component.
Among the embodiment 3, use the crushing medium of case hardness greater than solder flux.Such hardness makes the solder flux surface abrasion, compares with embodiment 1, and pollution rate improves.
According to the method for the processing waste printed circuit board of the invention described above first aspect, can suppress the pollution rate of solder flux, effectively separating metal and plate resin Composition.
(2) embodiment of second aspect present invention is described below with reference to accompanying drawing, from the method for waste printed circuit board separating metal material.
In the following embodiment, waste printed circuit board refers to: by on the copper-clad laminate that is layered in the Copper Foil on the base material, the plate by the printed substrate of circuit, by the printed substrate of the electronic component of assembling and the circuit formed or the printed substrate that electronic component all or part has been removed.Such printed substrate is the waste printed circuit board that the substandard products that produce from used product or production process and waste product are collected.The plate portion of printed substrate contains the plate resin Composition, and as epoxy resin, phenol resin, polyester or polyimides, the base material of plate is paper, glass cloth, non-woven glass fabric or nonwoven aromatic polyamide fabric.
The flow chart that is the present invention from the method for waste printed circuit board separating metal material shown in Figure 2.
The present invention shown in Figure 2 with heating steps, is cooling and pulverising step from the method for waste printed circuit board separating metal material subsequently, is separating step at last.In the final step, plate resin Composition and metal material separate as Copper Foil, solder flux and electronic component.Strictly speaking, electronic component often contains resin Composition.Yet in this embodiment, the electronic component of the resinous component of this class is defined as the part of metal material.
Heating, cooling, pulverizing and separating step are described below.
Heating steps is at first described.Heating steps uses electric furnace, infrared heater, far-infrared heater, induction heater or hot air gun.The band metal material is heated to 250 ℃ or higher temperature as the waste printed circuit board of solder flux and electronic component, but is lower than 500 ℃ (measuring the temperature of the plate portion of printed substrate).In heating steps, the plate resin Composition becomes fragility.
Heating steps should carry out in oxygen-lean atmosphere, avoiding the burning of plate resin Composition, and suppresses the oxidation of metal component.Oxygen-lean atmosphere refers to that oxygen concentration for example is 10% or lower atmosphere, comprises inert atmosphere.Exactly the plate resin Composition does not burn in oxygen-lean atmosphere, or suppresses the oxidation of metal component.Inert gas comprises rare gas (as helium and argon), nitrogen, carbon dioxide.Nitrogen because it handles convenient by preferably as inert gas.Oxygen-lean atmosphere also comprises the atmosphere under low pressure and the vacuum.Metal component can be added reducibility gas by under the thermal decomposition product oxidation situation of plate resin Composition in atmosphere, suppress this class oxidation as hydrogen.
When waste printed circuit board contains fire retardant, even can not burn, so heating steps can carry out in air owing to the printed substrate component heats also in air.
In above-mentioned heating steps, printed substrate is heated to 250 ℃ or higher temperature.This is that wiring board begins to become fragility because the plate resin Composition begins to decompose at 250 ℃ or higher temperature.When fragility improves with the temperature rising, plate resin Composition or additive on the waste printed circuit board, the thermal decomposition material that produces as fire retardant increases gradually.This class waste gas begins to be paid close attention to by people to the burden of environment.Therefore, at the decomposed substance of heating steps, labor its to the effect of environmental pressure and the relation of heating-up temperature.Therefore, when waste printed circuit board contains halide, during as the additive of organic bromide, the decomposed substance of hydrogen halides obviously increases being not less than under 500 ℃ the heating-up temperature.Lead reaction in hydrogen halides and the solder flux produces lead halide.This class material is dispersed in the waste gas.Therefore, heating-up temperature must be lower than 500 ℃.In addition, in the temperature that is not less than 500 ℃, begin to take place hydrogen halides and metal component, as the side reaction of Copper Foil.So heating-up temperature must be lower than 500 ℃, could guarantee to reclaim the quality of metal material.In a word, in the heating steps, waste printed circuit board is heated to 250 ℃ or higher temperature, but is lower than 500 ℃.
Particularly,, but be lower than the heat treated of 500 ℃ of temperature, and at 250 ℃ or higher temperature but be lower than to handle under 350 ℃ the temperature and compare, obviously shorten the needed time of processing that makes the waste printed circuit board embrittlement at 350 ℃ or higher temperature.
Cooling step is described below.The waste printed circuit board of heating steps heating is in this cooling step cooling.If the waste printed circuit board of heating steps heating is directly brought in the air, printed substrate may burn, and metal material can be oxidized.Therefore, be the burning of avoiding printed substrate and the oxidation of metal material, the waste printed circuit board after the heating steps heating is cooled off under oxygen-lean atmosphere at cooling step.Oxygen-lean atmosphere was described above.Cooling means comprises the natural cooling in the oxygen-lean atmosphere and spray the inert gas that is about room temperature on the waste printed circuit board of heating, as nitrogen.Need the cooling waste printed circuit board, to reduce temperature extremely as about 180 ℃, printed substrate can not burn under this temperature.
Pulverising step is described below.The fragility plate resin Composition of the waste printed circuit board that cools off in the cooling step is pulverized in pulverising step.When pulverizing the plate resin Composition, must suppress metal material, as the pulverizing of Copper Foil, solder flux and electronic component, with convenient plate resin Composition and the separating of metal material subsequently.Therefore, pulverising step of the present invention adopts the little method of crush force, and this method can suppress the pulverizing of metal material, and fully pulverizes the plate resin Composition.More specifically, a kind of in two kinds of methods below adopting: the particle impact operations, with the waste printed circuit board of many particles collisions through the heating steps processing; And the wall impact operations of waste printed circuit board impact walls.In these operations, the impulse force in each the impact is less, therefore can suppress the pulverizing to metal material such as electronic component.And it is broken as the fine powder of the metal material of copper and so on that the use of impulse force can suppress, and copper product is easy to fragmentation owing to it is very thin.Can not pulverize by these particle collisions or wall impact operations without the waste printed circuit board that heating steps is handled.Yet for the waste printed circuit board of handling through heating steps, their fragility makes these two kinds of operations can select to pulverize the plate resin Composition basically.On the other hand, some pulverizers that are generally used for conventional waste disposal are not optimized for pulverising step of the present invention.Such pulverizer includes the pulverizer of rotary cutter and the pulverizer (hammer crusher) of rotary hammer is arranged.These pulverizers are because of the excessive crushing metal material of its strong excessively crush force meeting, as electronic component, Copper Foil and solder flux.Excessive pulverizing like this can cause the difficulty that metal material subsequently separates and reclaims.
Particle impact operations recited above is described below for example.In the illustrative examples as shown in Figure 3, container 1 contains many particles 2 and through heat treated waste printed circuit board 3.Container 1 is pressed the direction rotation of arrow 4.Reach pulverizing by freely falling of particle 2.This equipment is called the lift-over ball mill.In another illustrative examples of particle impact operations as shown in Figure 4, container 1 contains many particles 2 and through heat treated waste printed circuit board 3.Container 1 is pressed the direction up-down vibration of arrow 4.Oscillating movement by particle 2 reaches pulverizing.This equipment is called vibrator.Move up and down though be illustrated in figure 4 as, also can adopt side-to-side movement, rotatablely move or the combination of these motions.As shown in Figure 5, also have the illustrative examples of a particle impact operations, it comprises uses as the injection apparatus 5 of compressed air with high velocity jet particle 2.Injection apparatus 5 is ejected into many particles 2 on heat treated waste printed circuit board 3 and pulverizes with collision.In these illustrative examples, use vibrator and particle spray unit to be advisable, pulverize because the high-speed motion of particle can reach at short notice.
The particle that uses in above-mentioned particle impact operations is made of ceramic material (as aluminium oxide and zirconia), metal material (as iron and stainless steel) and/or resin material.Use can obtain bigger crush force by the heavier particle that constitutes as ceramic and metal, therefore reaches bigger pulverizing speed.On the other hand, use the wearing and tearing that can suppress the metal material of waste printed circuit board as the lower material of the case hardness of resin.Core by pottery or metal are arranged and in surface coated the particle of resin can satisfy these two requirements preferably simultaneously.For granular size, too small particle has less crush force, so degradation rate is lower.And such particle can quicken the excessive pulverizing of Copper Foil, because Copper Foil is very thin and frangible, and less in the curvature of percussion point particle.In a word, the diameter of employed particle should be greater than 1 millimeter, better greater than 10 millimeters.And diameter is better greater than 20 millimeters particle, because such particle is bigger than most of electronic components, therefore, by screening effectively separating particles and electronic component in the described separating step below.Coating of particles does not have concrete restriction, but is advisable with sphere or analogous shape, because marginate particle can quicken the excessive pulverizing of Copper Foil.
The masked portion of printed substrate (shaded part) is positioned at as being difficult to pulverize near going between and the masked part.Yet according to above-mentioned particle impact operations, such masked portion is easy to pulverize, because the pulverizing point of particle is enough little.
In above-mentioned particle impact operations, a large amount of particles 2 is used to pulverize the plate resin Composition of waste printed circuit board 3.Yet available one or a spot of particle 2 are pulverized the plate resin Composition of waste printed circuit board 3.
With illustrative examples above-mentioned wall impact operations is described below.An illustrative examples as shown in Figure 6 comprises cylindrical container 1, container 1 have many be fixed on inwall vertically scrape the collection plate 6.Waste printed circuit board after the heat treatment is put into the container 1 of inclination.Container 1 is pressed the direction rotation of arrow 4.Waste printed circuit board 3 has been drawn by scraper plate 6, freely falls in container then, collides with the inwall of container 1 and/or with scraper plate 6.Collision mainly causes the plate resin Composition of waste printed circuit board 3 to be pulverized.This method preferably 1 be can guarantee that waste printed circuit board is drawn to play container 1 top, before freely falling pulverizing, can in rotary container 1, not slide.And from work angle, Fig. 6 configuration is preferably the pulverizing plate and the metal material that can spray the waste printed circuit board 3 of pulverizing from the outlet of container 1 continuously.In the illustrative examples of another wall impact operations as shown in Figure 7, the waste printed circuit board 3 after the heat treatment is rotated the dish throwing and still arrives wall 8.Waste printed circuit board and wall 8 collisions, thus the printed wire plate portion of waste printed circuit board is pulverized substantially.By the pressure collision of waste printed circuit board 3, improved the pulverizing speed of this method with wall 8.
Can implement such wall impact operations by simple equipment structure.Different with above-mentioned particle impact operations, this method does not need to go out from particle separation the metal material of recovery.
The fin of claim 5 of the present invention is assemblied in the inwall of cylindrical container, is used for pulverising step, and they can be the scraper plates 6 of Fig. 6.Although in the inwall of the cylindrical container 1 of Fig. 6, be equipped with a plurality of scraper plates 6, can be equipped with at least one scraper plate 6 at the inwall of cylindrical container 1.
Separating step is described below.In the separating step, the fine powder of the plate resin Composition of pulverizing at pulverising step separates with the metal material that not have pulverizing basically.The plate resin Composition mainly is ground into pulverous in the pulverising step, but metal material do not pulverized basically, remain bigger particle.The granularity difference of plate resin Composition and metal material makes and can effectively separate by screening.In the screening,, reclaim metal material on the sieve of 000 micron perforate, the general plate resin Composition that recovery is pulverized below the sieve of 100-500 micron perforate generally from 100-1.Also can separate,, material crushed is separated into metal material and plate resin Composition effectively as centrifugal, inertia and gravity classification by proportion.When isolated plate resin Composition contained some little sheet metals, further lock out operation separated the organic efficiency that can improve metal material as proportion.Behind the pulverising step, fail the bigger plate resin sheet of the printed substrate fully pulverized if leave some, these sheets can be separated by screening and send back to pulverising step and pulverize.
Therefore, metal material is easy to separate as Copper Foil, solder flux and electronic component.The metal material that reclaims can be used as salvage material, and waste printed circuit board becomes harmless simultaneously.
Next step is the recycling step of metal material, wherein, collects respectively according to shape separately at the isolated metal material of separating step.As shown in Figure 8, the angle tilt that the conveyer belt 9 that moves upward and horizontal plane become to be scheduled to.The isolated metal material of separating step is supplied with conveyer belt 9, then columniform metal material of separate collection and the metal material that is difficult to fall.More specifically, the metal material that is easy to fall falls on conveyer belt 9 easily as cylindrical electronic component (as aluminium electrolytic capacitor) and linear electronic component (as resistance), can be collected in the metal material gathering-device 10 that is easy to fall of bottom.In contrast, the metal material that is difficult to fall can fall on conveyer belt 9 hardly as the sheet (as Copper Foil) of plate shaped electronic component (as IC) and paper tinsel formula, can be collected in the metal material gathering-device that is difficult to fall at top.Apply vibration on tape and can improve separation rate.
Method according to further separation of shape and recovery metal material is because the following fact is achieved like this, it is metal material, original form as electronic component can be preserved in step of the present invention well, and become fragility, and can pulverize with less crush force at pulverising step at the heating steps printed substrate.
Except above-mentioned heating, cooling, pulverizing and metal material recycling step, can also comprise extra step from this embodiment of waste printed circuit board separating metal material.In an example steps, before heating steps, the electronic component (comprising lead-in wire) that can take off bigger electronic component and can produce harmful substance at heating steps.In another example steps, waste printed circuit board can be immersed in the decomposed liq before heating steps.This liquid contains at least a following material: ethylene glycol, propylene glycol, diethylene glycol, DPG, Isopropanediol and sodium hydroxide solution.By such impregnation process, resin Composition predecomposition of part plate or swelling, therefore, at heating steps, the plate resin Composition can become fragility at lower temperature with than the weakness reason time preferably and fully.The impregnation process step is carried out under higher temperature better, but because the decomposition and the swelling of accelerator card resin Composition part.The practical operation temperature of impregnation process is 50-300 ℃.
Above-mentioned embodiment comprises heating, cooling and pulverising step in order.Yet when waste printed circuit board did not contain solder flux, pulverising step can carry out simultaneously with heating steps.This is because the scattering of the solder flux that need not to consider to melt again.In another method, pulverising step can carry out under higher temperature, need not cool off waste printed circuit board behind heating steps basically.Equally, can not cool off waste printed circuit board and just carry out separating step.In this case, pulverize and/or separating step can carry out in above-mentioned oxygen-lean atmosphere, with the burning of avoiding printed substrate and the oxidation of metal material.In this case can pulverize or pulverising step after the plate resin Composition and the metal material of heat cooled down, carry out the recycling step of metal material then.The method of cooling hot plate resin Composition and metal material comprise above-mentioned in oxygen-lean atmosphere natural cooling method and on the plate resin Composition of heat and metal material, spray the inert gas that is about room temperature, as nitrogen, with the burning of avoiding printed substrate and the oxidation of metal material.To containing the printed substrate of halogen component (as chlorine and bromine) and/or antimony component fire retardant, when such waste printed circuit board keeps original shape through heat treatment, separate and the printed wire plate that reclaims can contain the residue of this class at pulverising step.
Consider to reclaim the last processing of back printed wire plate portion, according to the method for handling, halogen and antimony component may become the burden of environment.Therefore, require during reclaiming plate portion, to remove this class flame retardance element.
Therefore, the present invention comprises heating with meeting the requirements and removes step, wherein under the plate of the pulverizing of the waste printed circuit board that separates behind heating, pulverizing and the separating step can avoided the atmosphere of their burnings, be heated to 350 ℃ or higher temperature, remove fire retardant from waste printed circuit board thus.
The fire retardant that contains halogen and/or antimony component begins thermal decomposition about 250 ℃, noninflammability is provided.Therefore, in heating steps of the present invention, can discharge halogen and/or antimony component from wiring board.Yet in the heating steps of the original form of holding plate, the surface area of plate is little.And plate portion does not melt in this heating steps, because waste printed circuit board is by thermosetting resin, constitutes as phenolic resins and epoxy resin.So, even the heating by this step of halogen and/or antimony component also is difficult to overflow from wiring board.
By comparison, among the present invention, heating be the crushing piece of printed wire plate portion, therefore these sheets are separated at separating step, have bigger surface area.So, be easy to escape from wiring board by heating halogen and/or antimony component.
Need 350 ℃ or higher heating-up temperature in the heating steps of the present invention, so that remove halogen and/or antimony component.And heating must be carried out in the atmosphere that the crushing piece of printed substrate can not be burnt, with circulating printing wiring board part.Be advisable with oxygen-lean atmosphere.Yet to being lower than 500 ℃ heating and removing step, air also is acceptable.
Plumbous component be waste printed circuit board contained become one of material of environmental pressure, it mainly is present in the coating of lead-in wire and the solder flux that is used to assemble.Another source of plumbous component is the PVC stabilizer as covering resin, and so plumbous component exists with the form of subcarbonate, three alkali sulfates and lead stearate.
According to the present invention, a part of leaded component, fine powder is not broken as the coating of the lead-in wire of electronic component and the solder flux of assembling electronic component, therefore is easy to separate from the crushing piece of printed substrate, and reclaims as the metal material component.Yet the leaded component of another part was dispersed in the plate resin originally as the stabilizer of polyvinyl chloride.Therefore, when employing was of the present invention, this part leaded component was mixed in the sheet component of printed substrate parts of fine pulverizing.
On the other hand, the antimony component that contains of fire retardant is contained in the printed wire plate portion.This antimony component that contains also is dispersed in the plate resin, therefore, when employing is of the present invention, can be mixed in the sheet component of printed substrate parts of fine pulverizing.
Therefore, consider the circulation of the sheet component that printed substrate disperses, require the pollution of removing this ekalead and antimony.So, among the present invention, should dissolve and remove step, the wherein crushing piece water treatment of waste printed circuit board is from the crushing piece stripping heavy metal of waste printed circuit board.
The plumbous component meeting of stabilizer of polyvinyl chloride and so on and be to heat up in a steamer the hcl reaction that polyvinyl chloride thermal decomposition in the step produces.This reaction produces lead chloride.
When printed substrate contained bromine flame retardant, the thermal decomposition by the destructive distillation step can produce bromine gas and hydrogen bromide.These bromine materials can form lead bromide with plumbous component reaction.Therefore, in the destructive distillation step, halogen gas that thermal decomposition produces and hydrogen halide and plumbous component reaction produce lead halide.These lead halides are sneaked in the crushing piece of the printed wire plate portion that separating step reclaims.
Because these lead halides have sufficient solubility, so plumbous component is easy to crushing piece stripping from the printed wire plate portion by the stripping step, pulverizes and the sheet that separates with water treatment in the stripping step.The situation of antimony is same.In the destructive distillation step, halogen gas and hydrogen halide and antimony component reaction that thermal decomposition produces produce antimony halides.These antimony halides are sneaked in the crushing piece of the printed substrate that separating step reclaims.
Because these antimony halides also have sufficient solubility, according to the present invention, by the stripping step of water, such antimony component is easily from the crushing piece stripping of printed substrate.
Stripping step of the present invention comprises uses the appropriate addn that adds in the entry.The method of water treatment comprises the water-immersed method of printed wire plate portion that will separate, and in the method for the printed wire plate portion injection water that separates.
Embodiment
Describe the present invention in detail with specific embodiment below.
The composite plate that the waste printed circuit board of this embodiment (50 * 150 millimeters sizes) is made up of nonwoven glass fabric/glass cloth and epoxy resin.Plate substrate contains bromine flame retardant, and printed substrate mainly is assembled with IC, aluminium electrolytic capacitor, fixed resistance and connector.Useless printed substrate is put into 90 millimeters of diameters, and long 1000 millimeters ceramic boiler tube heated from the outside of pipe, 250 ℃ of insulations 120 minutes.After naturally cooling to 40 ℃, from pipe, take out waste printed circuit board, finish the heating and cooling step.In the heating and cooling step, in pipe, feed nitrogen with 3 liters/minute flows.In the pulverising step, and the use vibrator (Paint Shake, AsadaTekkoshyo Co., Ltd.).The vibration of ball mill is 640 cycles per minute, and amplitude is 8 millimeters.Waste printed circuit board after iron particle (20 millimeters scribble nylon resin) and the heat treatment is put into 130 millimeters of internal diameters, in the dark 180 millimeters cylindrical rustless steel container.Sieve with 200 microns of perforates sieves the comminution of material of acquisition, is separated into the metal material component (comprising electronic component) in plate resin Composition of collecting under the sieve and collection on sieve.
In addition two kinds of situations are carried out under the heating-up temperature of 350 ℃ and 450 ℃ equally respectively.A comparative example does not carry out the heating and cooling step.Two comparative examples carry out under 200 ℃ and 500 ℃ respectively in addition.Other condition is identical.The results are shown in table 2.Reach the required pulverizing of the definition time of better pulverizing required time according to wiring board.Carry out plumbous chemical analysis, measure the lead that is emitted to waste gas in the heating steps from solder flux.
Table 2
| Heating-up temperature (℃) | The pulverizing time that needs (minute) | Plumbous scattering | |
| Embodiment | 250 | 30 | Do not have |
| Embodiment | 350 | 10 | Do not have |
| Embodiment | 450 | 10 | Do not have |
| Comparative example | Not heating | Do not pulverize | - |
| Comparative example | 200 | Do not pulverize | Do not have |
| Comparative example | 500 | 10 | Measure |
As shown in table 2, when waste printed circuit board at 250 ℃ or higher temperature but be lower than 500 ℃ when handling, lead can dissipation in waste gas, the material after the pulverizing can be separated into plate resin Composition and metal material (electronic component, Copper Foil and solder flux) well.Particularly, 350 ℃ or higher, can shorten the required pulverizing time but be lower than 500 ℃ heating-up temperature.In contrast, not having heating or heating-up temperature is 200 ℃ comparative example situation, and wiring board does not become fragility, can not pulverize.When heating-up temperature is 500 ℃, in waste gas, detect plumbous dissipation.
The waste printed circuit board that this embodiment uses and embodiment 1 is same.Carry out the heating and cooling step similarly to Example 1.Heating-up temperature is 350 ℃.In the pulverising step, (Fuji SeisakusyoCo. Ltd.), behind the cooling step, sprays the nylon resin particle of 2 millimeters of diameters with the expulsion pressure of 0.5Mpa to use the injection process equipment.Sieve with 200 microns of perforates sieves the comminution of material of acquisition, is separated into the metal material component (comprising electronic component) in plate resin Composition of collecting under the sieve and collection on sieve.
Therefore, in pulverising step, wiring board was pulverized in about 5 minutes basically.In separating step subsequently, material crushed can be separated into plate resin Composition and metal material (electronic component, Copper Foil and solder flux) preferably.
The paper phenol plate that waste printed circuit board among this embodiment (50 * 150 millimeters sizes) has brown paper and phenolic resins to make.Plate substrate contains bromine flame retardant, is assembled with electronic component on the printed substrate, mainly is IC, aluminium electrolytic capacitor and fixed resistance etc.Identical with embodiment 1, carry out the heating and cooling step.Heating-up temperature is 350 ℃.In the pulverising step, adopt the wall impact operations, wherein, waste printed circuit board is put into predetermined bag, fall, repeat 50 times to the floor.Sieve with 500 microns perforates sieves the comminution of material that is obtained, and is separated into the metal material component (comprising electronic component) in plate resin Composition of collecting under the sieve and collection on sieve.Re-use the recycling step that conveyer belt carries out metal material.Conveyer belt moves upward with the belt speed of 150 mm/second, becomes 20 degree to tilt with horizontal plane.To supply with conveyer belt at the metal material that separating step is collected, reclaim metal material.
Therefore, wiring board is pulverized basically at pulverising step.Separating step material crushed subsequently is separated into plate resin Composition and metal material.And, reclaiming the metal material step, metal material is divided into and comprises aluminium electrolytic capacitor and one group of fixed resistance and comprise IC and a group of Copper Foil.
The paper phenol plate that waste printed circuit board among this embodiment (50 * 150 millimeters sizes) has brown paper and phenolic resins to make.Plate substrate contains bromine flame retardant, and printed substrate only has lead.Identical with embodiment 1, carry out the heating and cooling step.Heating-up temperature is 350 ℃.In the pulverising step, adopt the wall impact operations, wherein, only the waste printed circuit board of cooling is put into hydrostatic column (300 millimeters of internal diameters, dark 500 millimeters), have the miter angle of being separated by to be fixed on the scraper plate of inwall in the container, this container rotates with 500 rev/mins rotating speed.Sieve with 500 microns perforates sieves the comminution of material that is obtained, and is separated into the metal material component (Copper Foil) in plate resin Composition of collecting under the sieve and collection on sieve.
Therefore, wiring board is pulverized in about 10 minutes basically at pulverising step.In separating step subsequently, material crushed is separated into plate resin Composition and metal material (Copper Foil).
This embodiment uses the waste printed circuit board identical with embodiment 1.Printed substrate is immersed in 170 ℃ the ethylene glycol and carried out the impregnation process step in 2 hours.Afterwards, identical with embodiment 1, carry out the heating and cooling step.Heating-up temperature is 250 ℃.In the pulverising step, under the condition identical, use vibrator with embodiment 1.Sieve with 200 microns perforates sieves the comminution of material that is obtained, and is separated into the metal material component (comprising electronic component) in plate resin Composition of collecting under the sieve and collection on sieve.
Among this embodiment, the impregnation process before the heating steps will be pulverized the required time and shorten to 10 minutes, and be 250 ℃ situation in embodiment 1 heating-up temperature, and the time is 30 minutes accordingly.Afterwards, material crushed is separated into plate resin Composition and metal material (electronic component, Copper Foil and solder flux).
The plate resin Composition of under sieve, collecting among the superincumbent embodiment 3 of heat treatment.In this step, 90 millimeters of diameters, heating plate resin Composition in long 1000 millimeters the ceramic boiler tube was 350 ℃ of insulations 120 minutes.After being cooled to 40 ℃, from pipe, take out the plate resin Composition.During this step, in pipe, feed nitrogen with 3 liters/minute flows.
Measure this heating and remove the bromine content of step front and back.Heating and removing the preceding bromine content of step is that 5.5% (weight) is reduced to 0.1% (weight) in heating with after removing step.
Embodiment 7
The paper phenol plate that waste printed circuit board among this embodiment (50 * 150 millimeters sizes) has brown paper and phenolic resins to make.Plate substrate contains bromine flame retardant, is assembled with electronic component on the printed substrate, mainly is IC, aluminium electrolytic capacitor and fixed resistance etc., also has the lead-in wire of assembling.Identical with embodiment 1, heat, cooling, pulverizing and separating step.Heating-up temperature is 350 ℃.The plate resin Composition that acquisition is collected under sieve.The plate resin Composition that obtains mix with 10 times of water to its weight, in this stripping step, stir down and kept dipping 6 hours.Afterwards, by filtering the collecting board resin Composition, dry then.
The leaded component stripping of institute is in a kind of acid, with the plumbous component before and after this stripping step of ICP emission spectrometry in the plate resin Composition.Lead content is 0.2% (weight) before the stripping step, is reduced to 0.0003% (weight) after the stripping step.
Comparative example 1
Use the waste printed circuit board identical among this embodiment with embodiment 1.Identical with embodiment 1, carry out the heating and cooling step.Heating-up temperature is 350 ℃.In the pulverising step, and use hammer (formula pressure) broken machine (the H-12 type, Hosokawa Mikuron Co., Ltd.).Hammer (formula pressure) broken machine has a hammer that 2800 rev/mins of rotations are arranged.Sieve with 200 microns perforates sieves the comminution of material that is obtained, and is separated into the metal material component (comprising electronic component) in plate resin Composition of collecting under the sieve and collection on sieve.
As a result, electronic component is also broken by fine powder at pulverising step, and the plate resin Composition of collecting under sieve contains the pollutant of a lot of sheet metals, as the lead-in wire of Copper Foil and electronic component.In a word, separating metal material not yet in effect.
Therefore, a second aspect of the present invention provides from the method for waste printed circuit board separating metal component, wherein, and can be from the effective separating metal component of waste printed circuit board.
(3) embodiment of third aspect present invention is described below with reference to accompanying drawing, from the method for waste printed circuit board separating electronic components.
Waste printed circuit board in this embodiment refers to be assembled with the printed substrate of electronic component, to the assembling form without any restriction.This embodiment neither limits the particular type of electronic component, does not also limit the concrete material of wiring board.
According to this embodiment, be particle impact operations with the particles hit waste printed circuit board from the characteristics of the method for waste printed circuit board separating electronic components.
In the illustrative examples shown in Figure 9, hydrostatic column 1 contains many particles 2 and waste printed circuit board 3.Container 1 is pressed the direction rotation of arrow 4.Reach the bump of numerous particles 2 on waste printed circuit board 3 by freely falling of particle 2 with other motion.This equipment is called the lift-over ball mill.
In the illustrative examples of another particle impact operations shown in Figure 10, container 1 contains many particles 2 and waste printed circuit board 3.Container 1 is according to the direction up-down vibration of arrow 4.Reach the bump of numerous particles 2 on waste printed circuit board 3 by freely falling of particle 2 with other motion.This equipment is called vibrator.Although shown in Figure 10 for moving up and down, also can adopt side-to-side movement, rotate, or the combination of these motions.
As shown in figure 11, also have the illustrative examples of a particle impact operations, it comprises use compressed air, with the injection apparatus 5 of high velocity jet particle 2.Injection apparatus 5 sprays to waste printed circuit board 3 with numerous particles 2 and clashes into.
Using rotary drum ball milling and vibratory milling all is preferably, because their simple in equipment.
According to particle impact operations recited above, the coupling part of electronic component 60 and plate portion, promptly solder flux and lead-in wire are subjected to the impact of the impact of particle 2.Then, wiring board and electronic component are separately.It is because plate portion is to be made of toughness material that the selectivity of this coupling part disconnects, cracked hardly, and the part that is connected to electronic component is more weak under impact.In other words, the impact of particle 2 bump wiring boards is enough to make electronic component 60 and plate portion to disconnect, but not big to making plate portion cracked.Therefore, have only electronic component 60 and plate portion to separate basically, be easy to collect electronic component 60 like this.
Depend on the quality of each particle 2 and the collision rate that particle 2 strikes waste printed circuit board 3 by the above-mentioned 60 required times of particle impact operations separating electronic components.Quality and collision rate as fruit granule 2 are too little, and the impact of generation is not enough to disconnect electronic component 60 from wiring board.If quality and/or collision rate are too big, even plate also can be cracked.Therefore, the quality of the particle 2 of use and collision rate must rationally be set.For example, the lift-over ball mill uses bigger container 1, because this container has the bigger distance that falls, even light particle 2 also can obtain bigger collision rate.In contrast, vibrator and injection apparatus 5 originally just can quicken particle than lift-over ball mill more strongly, even therefore the small device structure also can obtain enough impacts.Yet too fast collision rate can cause the cracked of plate portion, and therefore, collision rate must rationally be set according to the quality of the particle 2 that uses, to avoid the cracked of plate portion.The quality of noting particle 2 depends on the size of each particle 2 and the material (density) of particle 2, and collision rate depends on the method for particle impact operations.
The size that requires particle 2 in this embodiment, for example, is positioned near the lead-in wire of electronic component 60 because big like this particle in the connecting portion branch that collision is sheltered difficulty takes place not too greater than electronic component 60, the coupling part of being sheltered by electronic component 60.Consider the size of normally used electronic component 60, the size that requires particle is 50 millimeters or littler.The particle of size is easy to impinge upon the coupling part between electronic component 60 and the plate portion like this, so that electronic component separates with plate.On the other hand, too small particle 2 light weight, impact is not enough.Therefore, require 5 millimeters or bigger particle.For example, by 10 mm granules that zirconia is made, it has bigger proportion, can disconnect electronic component 60.In contrast, less than 5 millimeters particle, its diameter is less than half of 10 mm granules, and quality owing to there are not enough impacts, can not effectively disconnect electronic component 60 less than 1/8 of 10 mm granules.This embodiment 1 that names a person for a particular job below describes in detail.
According to the scope of above-mentioned granular size, particle 2 should adopt the material of greater density.This is the particle of making because of by the material that larger specific gravity is arranged like this 2, even bigger quality is also arranged under reduced size, therefore, particle just has enough impacts.Particularly, can use following material: (density is 3.6 gram per centimeters to aluminium oxide
3), (density is 6.0 gram per centimeters to zirconia
3), (density is 2.2 gram per centimeters to silica
3), (density is 3.2 gram per centimeters to silicon nitride
3), (density is 3.1 gram per centimeters to carborundum
3), (density is 7.9 gram per centimeters to iron
3) and stainless steel (density is 7.9 gram per centimeters
3).The first five plants material is pottery, and all the other two kinds is metal.Zirconia, iron and stainless steel are because its high density is preferably.And having pottery or metal-cored particle can coating resin, as nylon or elastomeric material.
Such particle coating of particles is not specifically limited, but particle 2 is preferably sphere or analogous shape, because can avoid clashing into the Copper Foil that brings and the wearing and tearing of solder flux.And, in the mixture of the plate portion 100 that such spheric granules is easy to produce after impact operations, the electronic component 60 that separates and particle 2, separate with electronic component 60.That is, when the mixture of plate portion 100, particle 2 and electronic component 60 was supplied with as shown in figure 12 the conveyer belt 70 that moves upward, spheric granules 2 was collected in the particle collector 80 of bottom.On the other hand, electronic component 60 and plate portion 100 are compared with spheric granules 2 and to be difficult to fall, and are collected in the gathering-device 90 of the plate portion at top and electronic component mixture.Yet the electronic component 60 that a part has the shape that is easy to descend also is collected in the particle collection device 80.And, separate plate portion 100 and electronic component 60 in the gathering-device 90 of the mixture that all is collected in plate portion and electronic component, can use the conveyer belt of big gradient.When plate portion 100 and electronic component 60 supplied with such conveyer belt, be that the electronic component 60 that is easy to fall is collected in the bottom with respect to plate portion 100, and plate portion 100 is collected in the top.And, separate the particle 2 and the electronic component 60 that all are collected in the particle collection device 80, can use the less conveyer belt of gradient.When particle 2 and electronic component 60 supplied with such conveyer belt, be that the particle 2 that is easy to descend is collected in the bottom with respect to electronic component 60, and electronic component 60 is collected in the top.Yet,, and when separating particles 2 and electronic component 60, must rationally set the gradient and the belt speed of conveyer belt at separating plate part 100 and electronic component 60.In addition, when the reasonable gradient of having set conveyer belt as shown in figure 12 and belt speed, and when the mixture of plate portion 100, particle 2 and electronic component 60 is provided on tape, have only the particle 2 that very easily descends to be collected in the bottom.And when separating plate part 100 and electronic component 60,, plate portion 100 can separate them easily because, sieving operation greater than electronic component 60.
Below by specific embodiment the present invention is done detailed explanation.
The waste printed circuit board of present embodiment (being of a size of 70 millimeters * 90 millimeters) has the composite panel that is made by non-woven glass fabric/glass cloth and epoxy resin.This printed substrate mainly is equipped with integrated circuit (IC), aluminum electrolytic capacitor, fixed resistor and connector (connectors) on the one side of plate.It is that 130 millimeters, the degree of depth are 180 millimeters cylindrical rustless steel container that many 10 millimeters Zirconia particles and waste printed circuit board are put into internal diameter.(Paint Shaker, AsadaTekkoshyo Co. Ltd) vibrate this container to the vibrator that the vibration of use per minute is 640 times.The particle impact operations was carried out 5 hours.As a result, nearly all electronic component all separates from the composite material plate portion, and this composite panel is not cracked.Then, the mixture of the composite material plate portion, electronic component and the Zirconia particles that separate being delivered to the inclination angle is on the conveyer belt that moves upward of the speed with 150 mm/second of 10 ° belt conveyor.In the collecting part of bottom, collect Zirconia particles.In the collecting part at top, collect composite material plate portion and electronic component.After this, the mixture of the composite material plate portion collected in the collecting part of top and electronic component being delivered to the inclination angle is on the conveyer belt that moves upward of the speed with 150 mm/second of 30 ° belt conveyor.In the collecting part of bottom, collect electronic component.The composite material plate portion is collected in the collecting part at top.
Carry out the particle impact operations identical, but be to use 40 millimeters aluminium oxide particles to replace particle among the embodiment 1 with embodiment 1.Carried out about 3 minutes, nearly all electronic component all separates from the composite material plate portion, and the composite material plate portion is not cracked.After this, use the transport tape identical with embodiment 1 to operate, the mixture of composite material plate portion, electronic component and aluminium oxide particles is separated well and be collected in together separately.
Use waste printed circuit board in the present embodiment with embodiment 1 same type.(Ltd.) have internal diameter is that 1,250 millimeter, the degree of depth are 1,250 millimeter hydrostatic column to used rolling type ball mill for BM-1500, Chuo Kakouki Co..Many 10 millimeters stainless steel particles and waste printed circuit board are put into the container of the speed rotation of changeing with per minute 25.This particle impact operations was carried out 8 hours.As a result, nearly all electronic component all separates from the composite material plate portion, and this composite material plate portion is not cracked.After this, use the conveyer identical with embodiment 1 to operate, the mixture of composite material plate portion, electronic component and stainless steel particle is separated well and be collected in together separately.
Use waste printed circuit board in the present embodiment with embodiment 1 same type.The Zirconia particles that is of a size of 5 millimeters is ejected on the printed substrate particle impact operations 10 minutes to become 20 ° angle with the printed wire board plane with the jet velocity of 10 meter per seconds.The equipment that uses be spray processing machine (Fuji Seisakusyo, Co., Ltd.).As a result, nearly all electronic component all separates from the composite material plate portion, and the composite material plate portion is not cracked.After this, use the conveyor belts operation identical with embodiment 1, the mixture of composite material plate portion, electronic component and Zirconia particles can separate and be collected in together separately well.
A third aspect of the present invention provide a kind of from the waste printed circuit board the method for separating electronic components, electronic component can separate from waste printed circuit board effectively in the method.
(4) below with reference to the embodiment of description of drawings fourth aspect present invention.
(embodiment 1)
The distillation apparatus of the processing containing metal resin that is used for embodiment of the present invention 1 at first, is described with reference to Figure 13.
Figure 13 is the schematic diagram of distillation apparatus structure of processing containing metal resin that is used for the embodiment 1 of fourth aspect present invention.As shown in figure 13, box-shaped heating furnace 1A is equipped with the electric heater unit 2A that imbeds in this heating furnace furnace wall.Thermocouple 3A is the transducer that is used to measure temperature in the heating furnace 1A, and links to each other with temperature controller 4A, and this temperature controller is controlled the voltage that is applied on the electric heater 2A according to the temperature difference that records between temperature and the design temperature.Handling material 6A is made of metallic resin.Support 5A is placed in the heating furnace 1A, and material 6A is handled in carrying.The door 7A of heating furnace 1A can seal up heating furnace 1A.Nitrogen tube 8A links to each other with the nitrogen cylinder (not shown), by a plurality of injection orifice 9A with opening nitrogen is injected heating furnace 1A.Equipment of the present invention also comprises control valve 10A and Pressure gauge 11A, and the both is used for nitrogen.The 13A suction of cleaning fan is also removed the gas that heating furnace 1A produces, and 12A aspirates by the cleaning pipe, discharges via blast pipe 14A.Gas treatment cylinder 15A contains scrubber and charcoal absorption agent container, between cleaning pipe 12A and cleaning fan 13A.
Below explanation has said structure, is used for the operation that embodiment of the present invention 1 is handled the distillation apparatus of containing metal resin.Heating furnace 1A is undertaken temperature controlledly by thermocouple 3A and temperature controller 4A, its setting is make to handle the temperature of material 6A near 400 ℃.Be placed on processing material 6A among the heating furnace 1A and be the printed substrate that the epoxides of non-noninflammability grade makes, residual above it have a metal material, as solder flux, Copper Foil, resistor and capacitor.Heating furnace 1A makes promptly that by door 7A sealing extraneous air does not flow in the heating furnace.
In this case, begin to feed nitrogen to nitrogen tube 8A from not shown nitrogen cylinder.Then, nitrogen begins to inject heating furnace 1A by injection orifice 9A.Simultaneously, cleaning fan 13 begins to aspirate the gas that produces by cleaning pipe 12A from heating furnace 1A.Like this, the residual air among the heating furnace 1A is replaced by nitrogen, thereby heating furnace 1A inside has oxygen-lean atmosphere.
In this oxygen-lean atmosphere, heat treating materials 6A.Owing to be the oxygen deprivation environment, to handle material 6A thermal decomposition and oxidation reaction or burning do not take place, the resin material of handling among the material 6A (as epoxy resin) produces carbonizing gas.The carbonizing gas that is produced is aspirated away from heating furnace 1A subsequently and is discharged by cleaning fan 13A.Carbonizing gas during through the scrubber among the gas treatment cylinder 15A part carbonizing gas dissolving has taken place.Be removed in the charcoal absorption agent container of another part in gas treatment cylinder 15A.Therefore, neither contain cleaning exhaust gas (mainly being nitrogen) that combustible components and stink do not contain other harmful substance yet cleaning fan 13A and blast pipe 14A through the downstream.
Carry out aforesaid operations after one period scheduled time, closed control valve 9A.Stop simultaneously and clean fan 13A and electric heater 2A, open a 7A then.At this moment, on support 5A, be removed carbonizing gas component and carbonized resin.The metal part of originally staying on the printed substrate is still stayed on the printed substrate.
At this moment, carbonized resin has been lost original toughness, it be very fragility so that little crush force just can easily be pulverized it very thin.Therefore, the metal parts that is connected on the printed substrate can easily be removed and separate.
From heating furnace 1A, treated processing material 6A is taken out together with support 5A.After pulverizing, big part metal (as electronic component and copper conductor) can be by separating.The component of pulverizing very carefully can be separated by differential-density saparation, as air separation (using the air separation component).According to these methods, can be easily and accurately separating metal component and carbide.Can especially contain under the situation of a small amount of precious metal (as gold) economically as the raw metal of fusion process through the metal that separates at separated metal.Simultaneously, separated carbide ingredient contains metal component hardly, and they can be used as the sorbent material of sewage and Treatment of Sludge, and solid fuel or reduction processing material.Like this, according to the present invention, metallic resin can be recovered as useful raw material, and is difficult to handle them with conventional method by comparison.
As mentioned above, the distillation apparatus that is used to handle the containing metal resin according to embodiment of the present invention, the containing metal resin is after this processing of heating in oxygen-lean atmosphere too and becoming fragile thus, can separate easily and accurately separating metal component and carbide by screening or proportion, and, because the containing metal resin heats in oxygen-lean atmosphere, so the containing metal resin do not burn, and temperature is very high with regard to not becoming like this.Evaporation of metals and diffusion have been suppressed thus, even in resin, contain under the situation of low-melting-point metal (as the plumbous component of solder flux).
In embodiments of the invention, as long as will handle the heating and temperature control of material 6A in heating furnace 1A at 250 ℃ or higher according to the type of resin, the resin part will become fragile and become the carbonization state that can easily pulverize, need not the metal with the resin coexistence is carried out fusion again and curing again.Usually used resin is in 250 ℃ or higher and be lower than 500 ℃ and become fragile.Therefore, be preferably temperature is controlled at 250 ℃ or higher and be lower than 500 ℃, can save heat energy like this.Please note that setting in the heating-up temperature 500 ℃ of these upper limits is because a part of low-melting-point metal (as solder flux) and metallic resin can fusions when this ceiling temperature is above and be easy to evaporation and spread.As a result, need carry out exhaust-gas treatment owing to these metals.
(embodiment 2)
Embodiment of the present invention 2 below are described.The distillation apparatus that is used for the processing containing metal resin of the present embodiment has the basic structure of embodiment of being similar to 1.Yet heating furnace 1A is not the batch (-type) type with hermetically-sealed construction in the present embodiment.Different with it, the entrance and exit of handling material 6A all is to open wide all the time, handles material 6A and is on the platform that is placed on motion and transmit.Below Shuo Ming main emphasis point is difference.
Figure 14 is the schematic diagram of distillation apparatus structure that is used for the processing containing metal resin of the present embodiment.As shown in figure 14, the distillation apparatus that is used for the processing containing metal resin of the present embodiment comprises all the time to extraneous inlet 17Aa that opens wide of heating furnace 1A and outlet 17Ab, also comprise the conveyer 16A with wire netting pore area, it is via the arrow direction process heating furnace 1A of entrance and exit along Figure 14.Inlet 17Aa and outlet 17Ab comprise the flexible sheets 19A that is positioned near the outside, the both sides of heating furnace 1A.The support 5A that transports on the conveyer 16A has the wall 18A of inhibition gaseous diffusion as antetheca and rear wall for the direction of motion.
Below explanation has said structure, is used for the operation that the present embodiment is handled the distillation apparatus of containing metal resin.With being housed, the support 5A that handles material 6A puts into inlet 17Aa via flexible sheets 19Aa.Then, support 5A is automatically moved through heating furnace 1A by conveyer belt 16A.The processing material 6A that is contained on the support 5A handles with the method for destructive distillation that is similar to embodiment 1, automatically shifts out heating furnace 1A through outlet 17Ab and flexible sheets 19Ab until support 5.
Be equipped with under the situation of the printed substrate that the phenol of the non-noninflammability grade that contains fire retardant of electronic component makes handling material 6A, the decomposition gas of fire retardant is looped around the printed wire panel area in the process that heats printed substrate with heating furnace 1A.Thereby the atmosphere of printed wire panel area becomes oxygen-lean atmosphere.Therefore, contained resin Composition becomes fragility and printed substrate does not burn in the printed substrate, even atmosphere is also to be like this under the situation of oxygen rich gas (as air) in heating furnace 1A.Like this, contain at metallic resin under the situation of fire retardant, even externally be under the situation of oxygen-enriched atmosphere, the surrounding environment of containing metal resin also can keep the oxygen deprivation state.Therefore, need not to provide in addition inert gas (as nitrogen).This situation has advantage economically.
Because flexible sheets 19Aa, 19Ab have covered the major part of heating furnace 1A opening (17Aa and outlet 17Ab promptly enter the mouth), therefore flexible sheets 19Aa, the 19Ab opening that can suppress the carbonizing gas slave unit lets out, and do not disturb transporting of the support 5A that handles material 6A is not housed.
Covered the major part that heating furnace 1A opens wide the cross section on the direction of motion of support 5A owing to suppress the wall 18A of gaseous diffusion, the carbonizing gas that the wall 18A that therefore suppresses gaseous diffusion can suppress processing material 6A generation spills from opening (being the entrance and exit of heating furnace 1A).
Like this, the present embodiment has realized a kind ofly having the destructive distillation treatment facility of advantage in operation, is placed on the conveyer 16A as long as will handle material 6A, just can realize that continuous carbonization operates.
In the present embodiment, can use the flexible sheets 19Aa, the 19Ab that make by glass fabric/fluororesin, they can keep thermal endurance and flexibility, as long as the temperature of flexible sheets present position is no more than about 250 ℃.Surpass under 250 ℃ the situation in temperature, use sheet metal, as the sheet that gets by stainless steel, copper or aluminum.
In the structure of the present embodiment, the processing material 6A in the high temperature can take out from heating furnace 1A, carries out destructive distillation continuously because handle material 6A.In this case, can near heating furnace 1A back, lay a cooling device, be used for cooling off rapidly heated processing material 6A.According to this method, handle material 6A and can and promptly handle, and do not have the danger that the material that is in high temperature is exposed to air and lighted with the handling safety of separating, do not have other danger of combustion yet.The type of cooling comprises cryogenic gas or liquid directly is sprayed onto the method for handling on the material 6A, and the method that the sheet that is cooled or roller are contacted with processing material 6A.
These were handled material 6A and reach its heat decomposition temperature and produce near the position of carbonizing gas when in addition, the clean-out hatch of the cleaning pipe 12A processing material 6A that can be arranged on the support 5A institute splendid attire that is transmitted by conveyer 16A was heated in the process through heating furnace 1A.In this case, carbonizing gas can be removed by cleaning effectively, and can suppress the opening (be entrance and exit) of carbonizing gas by heating furnace 1A and let out.
In addition, this equipment can be equipped with hot media channel (heat medium channel), is used for cooling off a part of flexible sheets 19Ab.In this case, the heated processing material 6A after the destructive distillation when being sent, is fully being contacted in outlet with flexible sheets 19Ab.By contacting with this of flexible sheets 19Ab, effective heat exchange wherein also takes place with hot media channel in cooling processing material 6A effectively.
(embodiment 3)
Embodiment of the present invention 3 below are described.The distillation apparatus that is used for the processing containing metal resin of the present embodiment has the basic structure of embodiment of being similar to 2.Yet the present embodiment comprises the device that the processing material 6A that comes out is carried out post-processing operation from heating furnace 1A.Below Shuo Ming main emphasis point is difference.
Figure 15 is the schematic diagram of the major part structure of the present embodiment distillation apparatus of handling the containing metal resin.As shown in figure 15, the distillation apparatus that is used for the present embodiment processing containing metal resin comprises cutting roller 20A, is used to pressurize and shred the processing material 6A of process carbonization and fragility.Cutting roller 20A is located near the downstream of the conveyer 16A of work in the heating furnace 1A.This cutting roller 20A links to each other with the cooling water pipe 21A of cold water is provided to this roller.The equipment of the present embodiment comprises the collection basket 22A that is positioned at cutting roller 20A downstream, is used to collect fragment chopped.
Below explanation has said structure, is used for the operation that the present embodiment is handled the distillation apparatus of containing metal resin.The resin of the process processing material 6A that destructive distillation is handled in heating furnace 1A partly has been carbonized, and it is very crisp so that can easily with little pressure it be shredded.Therefore, reel between the cutting roller 20A that material 6A is being near the rotation the heating furnace 1A outlet and during pressurized, carbonized resin is partly very easy to be shredded and pulverize when handling.The metal part that partly coexists with carbonized resin in this process is separated or strip down, and falls into carbonized resin part and collects basket 22A.
Separate or air separation can be easily and promptly will collect chip separation chopped collected among the basket 22A and become carbonized resin and metal by classification, and need not any other disintegrating apparatus.
Like this, the present embodiment has realized a kind of destructive distillation treatment facility, and this equipment carries out more effectively carrying out the continuous chopping process of separation process subsequently, and wherein chopping process continuously is to be undertaken by the processing material that cutting roller 20A chopping is handled through destructive distillation.
In the present embodiment, can provide cold water by cold water pipe 21A to cutting roller 20A.In this case, handle material 6A if heated words just can be cooled by cutting roller 20A immediately after coming out from heating furnace 1A.
Though in each embodiment of the present invention, all use electric heater, yet heater of the present invention is not limited to this as heater.Heater comprises the combustion heat that uses pipeline gas fuel (as town gas and propane gas) or liquid fuel (as kerosene).In order to use the combustion heat, can add a feeder (as air blast) if necessary and be used for burning.Using under the situation of liquid fuel, specifically is the device that adds the liquid fuel that is used to vaporize in the upstream of heater (being burning zone).
The method of the processing carbonizing gas that carries out in gas treatment cylinder 15A comprises flame combustion, catalytic combustion and catalytic oxidation.Catalyst is used in latter two reaction.The present invention is not limited to specific catalyst material and shape, can comprise for example sintered ceramic and metal; Honeycomb metal works and fabric; And the braid of ceramic fibre.The present invention also comprises for example curved surface shaped, cylindrical, waveform and plate shaped.These shapes of catalyst can at random be selected according to the processability and the purposes of material.About the activity of such catalysts component, the present invention includes platinum family noble metal for example commonly used, as platinum, palladium and rhodium; The mixture of these noble metals; Other metal and oxide thereof; And their mixture.The material of catalyst can based on fuel type and service condition select arbitrarily.
Around will the containing metal resin, remain oxygen deprivation, as common use nitrogen atmosphere as described in the enforcement scheme 1.In addition, can use other inert gas, as carbon dioxide, helium and argon.The present invention is not limited to specific gas atmosphere, as long as this gas atmosphere can prevent the burning of containing metal resin.For example, contain under the situation of fire retardant, can in the process of heat treated, realize the oxygen deprivation state, even also be like this under oxygen containing atmosphere at containing metal resin as described in enforcement scheme 2.Because the decomposition gas of fire retardant be looped around the containing metal resin around.In addition, reduce cleaning speed so that the carbonizing gas retaining ring that the containing metal resin produces around the containing metal resin, then the containing metal resin around can keep oxygen deprivation.
The containing metal resin that can handle according to the present invention can be any resin material that contains metal.This metallic resin comprises the printed substrate that for example has the copper wiring case, and this printed substrate also is equipped with electronic component.Please note the printed substrate in this specification or abbreviate wiring board as and generally include these printed wiring boards.In addition, the containing metal resin of handling according to the present invention comprises part and the assembly that contains the containing metal resin.Its example is that wherein motor or transformer is with resin moulded assembly.
Temperature measuring equipment in each embodiment of the present invention is a thermocouple.Yet temperature measuring equipment of the present invention is not limited thereto.For example, thermistor can be used, any amount of temperature measuring equipment can be used anywhere.In addition, be used for electrically heated voltage being controlled, and be used to the to burn fuel of heating and the delivery rate of air are controlled with the control device of temperature measuring equipment cooperation control heating power.Clearing apparatus is fan normally, but can be pump also if necessary, is used to provide the ability of pressurization or suction.
Conveyer in each embodiment of the present invention is the band that moves that is made by heat proof material (as metal).Yet conveyer of the present invention is not limited to this.For example, can use a series of rotary bar (roller).The drive unit that is used for drive transmission unit is electro-motor normally.
Gas treatment equipment in each embodiment of the present invention has the charcoal absorption container that is used to adsorb the adsorbent of carbonizing gas with the scrubber or comprise of spray liquid in the carbonizing gas with absorbing.Yet gas treatment equipment of the present invention is not limited thereto.For example, can use bubbling groove (bubbling tank), be used for carbonizing gas is spurted into absorption with in the liquid.These devices can also be used in combination.In addition, other possible gas treatment equipment is the decomposition reactor that is used for the destructive distillation decomposition reaction, uses the combustion reactor of flame combustion or catalytic combustion, and contain in addition can with the catalytic reactor of the decomposition catalyst of low density gas reaction.This gas treatment equipment can and be convenient to the property handled according to the state that uses and at random be selected.
Thus, a fourth aspect of the present invention provides a kind of being used for by destructive distillation the equipment of its carbonization is handled and made to the containing metal resin, and it is separating metal and resin carbonation thing easily.
(5) be illustrated below with reference to the embodiment of accompanying drawing fifth aspect present invention.
Enforcement of the present invention needs air feed and control device, the measurement mechanism of catalyst temperature, the transmission of waste material of the interior temperature controlling device of heater, heating furnace, clearing apparatus, air and the fuel of heating furnace to dispose, and the drive unit that transmits configuration.Heater comprises electric heater and uses the burning type heating unit of liquid or gaseous fuel.Be used to measure the temperature measuring equipment of temperature and catalyst temperature in the gas retort and be occasionally thermistor of any amount of thermoelectricity that can be placed on Anywhere.Be used for controlling the air of heating power and the supply and the control device of fuel controlled the voltage or the frequency of valve with electrically motorized operation and air blast with the temperature measuring equipment cooperation.Clearing apparatus is fan normally, but can be pump also if necessary, is used to provide the ability of pressurization or suction.Conveyer can be the heating resisting metal band of motion, or a series of rotary bar (roller).The drive unit that is used for drive transmission unit is electro-motor normally.These devices are conventional equipments, also can use other existing apparatus.Therefore, omitted technical descriptioon in this specification to these devices.
(embodiment 1)
The distillation apparatus that is used for waste disposal of embodiment of the present invention 1 is described with reference to Figure 16.
Figure 16 is the schematic diagram of the distillation apparatus structure that is used for waste disposal of the present embodiment 1.As shown in figure 16, the heating furnace 1B of similar tunnel-shaped is equipped with the electric heater 2B that is embedded in its furnace wall.Furnace temperature transducer 3B is the transducer that is used for measuring temperature in the heating furnace 1B, and 4B is connected with temperature controller, and this controller basis records the temperature difference between temperature and the design temperature and controls applied voltage on the electric heater 2B.Conveyer belt 5B is positioned at the wire netting pore area that heating furnace 1B is used to transmit waste material.Roller member 6B drives conveyer belt 5B.Cleaning pipe 7B has the end openings that is positioned at heating furnace 1B inside, and suction is also discharged carbonizing gas.Cleaning pipe 7B is communicated with gas purification parts 9B, blast pipe 10B and the ventilating fan 11B in downstream.Ventilating fan 11B has the exhaust end 12B that is positioned at its downstream.Gas purification parts 9B contains the oxidation catalyst 13B with ceramic honeycomb, and its load has the oxidation activity component of flammable organic material.In the inside of gas purification parts 9B, be positioned at the downstream of oxidation catalyst 13B around the heat-exchanging part 14B of cleaning pipe 7B.Cartridge 15B provides fuel gas (being LP gas) in the present embodiment, and controls flow fuel with fuel control valve 16B.Catalyst-temperature pickup 17B contacts with oxidation catalyst 13B, and signal is sent among the combustion controller 18B.Subsequently, combustion controller 18B produces signal and controls fuel control valve 16B.
The below operation and the effect of explanation the present embodiment.Heating furnace is that row control is compressed in electricity consumption, use the temperature that records at furnace temperature transducer 3B place by temperature controller 4B with stove in temperature be set near 400 ℃.The waste material that will contain a large amount of organic materials is put into heating furnace 1B as waste printed circuit board, rubbish, fish/vegetables leftover bits and pieces etc.Waste material transmits on the conveyer belt 5B that is driven by roller member 6B, moves through the inside of heating furnace 1B.Along with temperature uprises, waste gas and thermal decomposition material have been produced by waste material.The gas of these generations (carbonizing gas) aspirates by cleaning fan 11B, and 7B discharges via the cleaning pipe.The carbonizing gas that flows into cleaning pipe 7B is admitted among the gas purification parts 9B, purifies rapidly by oxidation.The temperature that please notes oxidation catalyst 13B keeps enough highly to be used for oxidation because of the fuel gas of supplying with by cartridge 15B.The fuel gas that the initial heating of oxidation catalyst 13B is to use to be provided by cartridge 15B carries out.After reaction, exhaust flow is arranged to atmosphere then through blast pipe 10B, ventilating fan 11B and exhaust end 12B.
Downstream at oxidation catalyst 13B produces hot waste gas.Yet these heats are collected by the heat-exchanging part 14B around the cleaning pipe 7B, thereby the waste gas that is cooled reaches ventilating fan 11B, and carbonizing gas just was preheated and performed the preparation of reaction before being admitted to oxidation catalyst 13B simultaneously.Even therefore contain under the situation of the component that is difficult to oxidation, also can easily realize the complete oxidation of carbonizing gas at carbonizing gas.The temperature of oxidation catalyst 13B is measured with catalyst-temperature pickup 17B all the time, is lower than under the situation of predetermined value in the temperature of oxidation catalyst 13B, opens fuel control valve 16B more by combustion controller 18B, so that more fuel to be provided.Under opposite situation, when the combustion heat owing to carbonizing gas made that too much the temperature of oxidation catalyst 13B is higher than predetermined value, 16B turned down with fuel control valve, to reduce fuel.Like this, the temperature of oxidation catalyst 13B just remains optimum value.
Oxidation catalyst 13B goes up fuel and the required air (oxygen) of carbonizing gas oxidation is introduced via cleaning pipe 7B with enough speed with carbonizing gas, because the entrance and exit of the conveyer belt 5B of heating furnace 1B opens wide atmosphere.Therefore, needn't provide air extraly.The content of imflammable gas can be dependent on type, amount and the state (variablees of aspects such as water content, pressurized) of sending into waste material and significant the variation is taken place in the amount of the carbonizing gas that is produced, the especially carbonizing gas.Yet, as long as keep essential catalyst temperature,, use the catalytic reaction of oxidation catalyst 13B also can realize reacting completely substantially even for low density gas, therefore can prevent to produce unburned material or intermediate materials.
Figure 17 shows an example of this equipment work characteristic in practical operation.Significant variation takes place in the flow (illustrating with solid line among the figure) of the imflammable gas that is produced by waste material in time.Yet the fuel supply flow is to carry out grading control by the temperature of oxidation catalyst 13B, and this temperature is maintained in the essential and enough temperature ranges that are used for work.Therefore, the amount of detection and identification carbonizing gas (mixture of various ingredients) or type are unnecessary for keeping exhaust gas cleaning.Singly be that to control fuel gas roughly according to the temperature of oxidation catalyst 13B just enough.
Anticipate multiple polluter is arranged in the waste material.Especially the pollution of chloride (comprising salt etc.) and halide (comprising plastic sheet etc.) can produce harmful dioxin in about 300-700 ℃ temperature range.
Therefore, the temperature of oxidation catalyst 13B is remained on 800 ℃ or higher, dioxin will thermal decomposition, thereby can prevent to discharge dioxin.Because the effect of heat-exchanging part 14B, in the downstream of oxidation catalyst 13B, temperature can be reduced to 300 ℃ or lower rapidly, therefore also can prevent to produce dioxin again by the decomposition gas of dioxin.Ceiling temperature is confined to be generally 1000 ℃ or lower in the heat resisting temperature scope of oxidation catalyst 13B.Because waste gas is cleaning and complete oxidation, can be equipped with a water-cooled heat exchanger in the downstream of gas purification parts 9B if necessary waste gas further is cooled to 200 ℃ or lower.
Because the residue that discharges behind the carbonizing gas is carbonized, and its volume is reduced to 1/7 or 1/4 of initial volume, therefore, even when these residues when so disposing, also can realize the remarkable reduction of volume.In addition, these residues can be used as betterment of land material and fertilizer, perhaps are used for the sorbing material of sewage and Treatment of Sludge, and solid fuel or reduction processing material.Like this, according to the present invention, can be recycled as useful raw material with the reluctant waste material of conventional method.
(embodiment 2)
Embodiment of the present invention 2 below are described.The distillation apparatus that is used for waste disposal of the present embodiment has similar basic structure and the mode of operation of distillation apparatus that is used for waste disposal with embodiment 1.Yet, in the present embodiment, be different from embodiment 1 to the control of atmosphere state in the heating furnace 1A with to the air fed device of carbonizing gas.Below Shuo Ming main emphasis point is these differences.
Figure 18 is the schematic diagram that the present embodiment is used for the distillation apparatus structure of waste disposal.As shown in figure 18, near every place of heating furnace 1B entrance and exit, be equipped with the air inlet pipe 8B that is used to supply with nitrogen.The flow that air inlet pipe 8B supplies with nitrogen surpasses by cleaning the flow of the carbonizing gas of managing the 7B suction and discharging.Air supply pipe 19B is connected the upstream end of gas purification parts 9B with cartridge 15B.
In such structure, in being full of the heating furnace 1B of nitrogen, add heat waste, prevented thus owing to the reaction with the gas that produced of heating causes the danger of lighting.In addition, suppress the oxidative polymerization in heating furnace 1B, prevented the generation of dioxin.Because the necessary air of carbonizing gas oxygen-free reaction (oxygen) that produces, so air supply pipe 19B is herein forced the air of enough flows is mixed with carbonizing gas in the upstream of air cleaning member 9B.Like this, carbonizing gas becomes flammable mixtures, on oxidation catalyst 13B oxidation reaction can take place.The essential heating furnace 1B of surpassing of the supply flow rate of air produces the expectation maximum stream flow of imflammable gas.Because can allow the imflammable gas content of relative broad range for reaction with oxidation catalyst 13B, thus the supply of air needn't fine be regulated according to fired state, can excessive consistently air feed.
The gas that adds heating furnace 1B by air inlet pipe 8B is used for reducing oxygen concentration.Therefore, as long as can meet the demands, needn't use clean gas (as nitrogen).For example, the waste gas with low oxygen content can be used by reclaiming from blast pipe 10B.This is simple in structure, economical, and does not hinder realization effect of the present invention.
Though it is of the present invention all to be to use electric heating to illustrate in the embodiment of the distillation apparatus that is used for waste disposal, obviously the present invention is not limited to this.Can also realize effect of the present invention with following alternative.
Heater can use the combustion heat of pipeline gas fuel (as town gas and propane gas) or liquid fuel (as kerosene).In order to use the combustion heat, can add a feeder (as air blast) if necessary to be used for burning.Using under the situation of liquid fuel, specifically is the device that adds the liquid fuel that is used to vaporize in the upstream of heater (being burning zone).
About the structure of the oxidation catalyst 13B that adorned among the gas purification parts 9B, used the base material of ceramic honeycomb in the present embodiment.Yet the present invention is not limited to specific catalyst material and shape, can comprise for example sintered ceramic and metal; Honeycomb metal works or metal fabric; And the braid of ceramic fibre etc.The present invention for example also comprises curved surface shaped, cylindrical, waveform etc., and plate shaped.These shapes of catalyst can at random be selected according to the processability and the purposes of material.About the activity of such catalysts component, the present invention includes platinum family noble metal for example commonly used, as platinum, palladium and rhodium etc.; The mixture of these noble metals; Other metal and oxide thereof; And their mixture.The material of catalyst can based on fuel type and service condition at random selected.
Thus, a fifth aspect of the present invention provides a kind of equipment that is used for waste disposal, use this kind equipment will contain the waste material destructive distillation and the carbonization of flammable organic material, its weight is descended, use this kind equipment can also obtain to be widely used as the carbonized product of recycled materials, wherein the carbonizing gas that is produced is purified fully by oxidation, becomes the waste gas of cleaning.
Claims (22)
1. method of handling waste printed circuit board, this method comprises the following steps:
In the heating of 250 ℃ or higher temperature, with destructive distillation its at least part surface leave the waste printed circuit board of the Copper Foil of solder flux;
Pulverizing is material after the destructive distillation of the described waste printed circuit board that described heating steps obtains; With
To after the pulverizing of the described waste printed circuit board that described pulverising step obtains, separating substances be the resin Composition and the metal component of plate.
2. the method for processing waste printed circuit board as claimed in claim 1 is characterized in that carrying out described pulverising step and will avoid described solder flux to be broken into particle less than 100 microns by fine powder.
3. the method for processing waste printed circuit board as claimed in claim 1 or 2 is characterized in that by using case hardness to carry out described pulverising step less than the ball mill grinding method of the crushing medium of solder flux.
4. method from waste printed circuit board separating metal material, this method comprises the following steps:
Under the partially combusted atmosphere of the printed substrate of avoiding described waste printed circuit board, or under the atmosphere of avoiding described metal material oxidation, be heated to the waste printed circuit board of rare metal material, make the temperature of described at least printed wire plate portion reach 250 ℃ or higher, but be lower than 500 ℃;
Only will be ground into the sheet that is no more than pre-sizing at the printed wire plate portion of the described waste printed circuit board of described heating steps heating; With
According to the difference in size of described crushing piece and described metal material, be separated in the crushing piece and the described metal material of staying on the described waste printed circuit board of the described main printed wire plate portion of pulverizing in the described pulverising step.
5. the method from waste printed circuit board separating metal material as claimed in claim 4 is characterized in that
Described pulverising step is to be undertaken by the main printed wire plate portion of described waste printed circuit board that the predetermined bump of particle on described waste printed circuit board pulverized in described heating steps heating.
6. the method from waste printed circuit board separating metal material as claimed in claim 5, it is characterized in that by the waste printed circuit board and the described particle of described heating are put into a container, rotation and/or vibrate described container and is further carried out described pulverising step by the described waste printed circuit board of described particles hit.
7. the method from waste printed circuit board separating metal material as claimed in claim 5, it is characterized in that the injection apparatus that can spray described particle at a predetermined velocity by providing, by described injection apparatus described particle jetting is arrived the waste printed circuit board of described heating, and further carry out described pulverising step by the described waste printed circuit board of described particles hit.
8. the method from waste printed circuit board separating metal material as claimed in claim 4 is characterized in that
Described pulverising step is by being provided at its inwall the hydrostatic column of rib to be arranged vertically;
To put into described container at the described waste printed circuit board of described heating steps heating;
Rotate described container, make described waste printed circuit board clash into the inwall and/or the described rib of described container;
Thereby the main printed wire plate portion of pulverizing described waste printed circuit board carries out.
9. the method from waste printed circuit board separating metal material as claimed in claim 4 is characterized in that
Described pulverising step is that the described waste printed circuit board in described heating steps heating is fallen to predetermined object, makes described waste printed circuit board strike described object;
Thereby the main printed wire plate portion of pulverizing described waste printed circuit board carries out.
10. as the described method of arbitrary claim among the claim 4-9, it is characterized in that carrying out described heating steps, make the temperature of described at least printed wire plate portion reach 350 ℃ or higher from waste printed circuit board separating metal material.
11. the method from waste printed circuit board separating metal material as claimed in claim 4, this method are included in the step of the described waste printed circuit board of cooling after described heating steps heating behind the heating steps; With
It is characterized in that in described pulverising step, pulverizing at the main printed wire plate portion of the described waste printed circuit board of described cooling step cooling.
12. the method from waste printed circuit board separating metal material as claimed in claim 11, it is characterized in that under the partially combusted atmosphere of the printed substrate of avoiding described waste printed circuit board, or under the atmosphere of the described metal material oxidation of avoiding described waste printed circuit board, carry out described cooling step.
13. the method from waste printed circuit board separating metal material as claimed in claim 4, before it is characterized in that this method is included in heating steps, the described waste printed circuit board that will have at least metal material immerses the step in the decomposed liq that contains at least a following material, and these materials are ethylene glycol, propylene glycol, diethylene glycol, DPG, Isopropanediol and sodium hydroxide solution.
14. the method from waste printed circuit board separating metal material as claimed in claim 4 is characterized in that this method comprises the following steps:
The belt conveyer that moves upward and be inclined relative to horizontal is provided;
To be provided to described belt conveyer at the described metal material that described separating step separates;
Collect step at metal, collect in the bottom of described belt conveyer and have the part that makes its shape that is easy to land in the described metal material; With
Collect step at described metal, collect at the top of described belt conveyer and have the part that makes its shape of landing hardly in the described metal material.
15. the method from waste printed circuit board separating metal material as claimed in claim 4, it is characterized in that this method comprises heating and removes step, heating makes the temperature of described fragment at least reach 350 ℃ or higher at the fragment of the described main printed wire plate portion of separating step separation in this step; Thereby in described heating with remove step and remove described fire retardant from described fragment.
16. the method from waste printed circuit board separating metal material as claimed in claim 4, it is characterized in that this method comprises from the step of described fragment stripping heavy metal, the described fragment of the described main printed wire plate portion that separates at described separating step is contacted with water.
17. the method from the waste printed circuit board separating electronic components, this method comprises the following steps:
By the particle impact operations, make predetermined particles hit be assembled with the waste printed circuit board of electronic component;
In described particle impact operations, disconnect the plate portion of described waste printed circuit board and being connected of described electronic component, the described plate portion on the described waste printed circuit board does not split substantially; With
In described particle impact operations, separate described electronic component from described waste printed circuit board.
18. the method from the waste printed circuit board separating electronic components as claimed in claim 17, it is characterized in that by described waste printed circuit board and described particle are put into predetermined container, rotation and/or vibrate described container and is further carried out described particle impact operations by the described waste printed circuit board of described particles hit.
19. the method from the waste printed circuit board separating electronic components as claimed in claim 17, it is characterized in that the injection apparatus that can spray described particle at a predetermined velocity by providing, with the waste printed circuit board of described particle jetting, and further carry out described particle impact operations by the described waste printed circuit board of described particles hit to described heating.
20., it is characterized in that particle diameter separately is 5 millimeters or bigger, but be no more than 50 millimeters or littler as the described method of arbitrary claim among the claim 17-19 from the waste printed circuit board separating electronic components.
21. the method from the waste printed circuit board separating electronic components as claimed in claim 17 is characterized in that this method comprises the following steps:
The belt conveyer that moves upward and be inclined relative to horizontal is provided;
The mixture of the described waste printed circuit board of all or part, described electronic component and described particle is provided to described belt conveyer;
Bottom at described belt conveyer is collected described particle at least; With
Collect the plate portion of described waste printed circuit board at the top of described belt conveyer, and have the part that makes its shape that is easy to land in the described electronic component at least.
22. the method from the waste printed circuit board separating electronic components as claimed in claim 17 is characterized in that this method carries out as the pre-treatment step from the method for waste printed circuit board separating metal material.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35307998 | 1998-12-11 | ||
| JP353,079/1998 | 1998-12-11 | ||
| JP037,959/1999 | 1999-02-17 | ||
| JP3795999 | 1999-02-17 | ||
| JP9945599A JP2000294919A (en) | 1999-04-06 | 1999-04-06 | Method for separating electronic component from rejected printed board |
| JP099,455/1999 | 1999-04-06 | ||
| JP223,101/1999 | 1999-08-05 | ||
| JP22310199A JP2001049355A (en) | 1999-08-05 | 1999-08-05 | Apparatus for dry distillation of metal-containing resin |
| JP223,381/1999 | 1999-08-06 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN03104381A Division CN1433851A (en) | 1998-12-11 | 2003-02-10 | Dry distillation apparatus for waste treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1260250A CN1260250A (en) | 2000-07-19 |
| CN1115210C true CN1115210C (en) | 2003-07-23 |
Family
ID=27460504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99126403A Expired - Fee Related CN1115210C (en) | 1998-12-11 | 1999-12-13 | Method for separating metal material from waste printed circuit board and destruction distillation apparatus for processing waste materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1115210C (en) |
Cited By (3)
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| CN100447263C (en) * | 2007-01-19 | 2008-12-31 | 王威平 | Harmless processing system and process for copper powder containing organism and glass fiber |
| CN112153818A (en) * | 2020-10-14 | 2020-12-29 | 杭州建德睿夕电子科技有限公司 | Device capable of automatically recycling electric elements on waste circuit board |
| US20220062962A1 (en) * | 2019-02-28 | 2022-03-03 | Mitsubishi Materials Corporation | Method for treating waste electronic substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3785540B2 (en) * | 2003-01-16 | 2006-06-14 | 株式会社Ａ．Ｐ．Ｒ | Disposal method of scrap car |
| CN100503061C (en) * | 2004-12-08 | 2009-06-24 | 浙江丰利粉碎设备有限公司 | Grinding recovery treatment technology of waste electronic wiring board and its equipment |
| CN102159735A (en) | 2008-08-20 | 2011-08-17 | P-燃料有限公司 | Disposal of electrical and electronic equipment |
| CN101987386B (en) * | 2009-07-31 | 2013-01-09 | 群联电子股份有限公司 | Dismounting device, dismounting method and dismounting system of ferromagnetic IC (Integrated Circuit) components |
| CN104096704A (en) * | 2013-04-03 | 2014-10-15 | 中国科学院生态环境研究中心 | Enrichment method for palladium in waste circuit board |
| WO2015032019A1 (en) * | 2013-09-03 | 2015-03-12 | Linde Aktiengesellschaft | Cryo-smashing of waste pcb |
| CN103599921A (en) * | 2013-11-19 | 2014-02-26 | 西南科技大学 | Automatic lossless dismounting recovery method and automatic lossless dismounting recovery device of discarded printed circuit board |
| CN103949461B (en) * | 2014-04-29 | 2016-05-11 | 哈尔滨工业大学 | A kind of method that uses near-critical water to separate and reclaim the each component material of waste and old circuit board |
| CN106564897A (en) * | 2015-10-08 | 2017-04-19 | 中国科学院过程工程研究所 | Method for preparing porous active carbon by using waste PCB |
| CA3090225C (en) * | 2018-01-31 | 2023-10-24 | Jx Nippon Mining & Metals Corporation | Processing method for electronic/electric device component waste |
-
1999
- 1999-12-13 CN CN99126403A patent/CN1115210C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100447263C (en) * | 2007-01-19 | 2008-12-31 | 王威平 | Harmless processing system and process for copper powder containing organism and glass fiber |
| US20220062962A1 (en) * | 2019-02-28 | 2022-03-03 | Mitsubishi Materials Corporation | Method for treating waste electronic substrate |
| CN112153818A (en) * | 2020-10-14 | 2020-12-29 | 杭州建德睿夕电子科技有限公司 | Device capable of automatically recycling electric elements on waste circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1260250A (en) | 2000-07-19 |
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