CN108160683A - A kind of method that waste and old tin plating copper-clad plate resource utilization utilizes - Google Patents
A kind of method that waste and old tin plating copper-clad plate resource utilization utilizes Download PDFInfo
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- CN108160683A CN108160683A CN201810116172.3A CN201810116172A CN108160683A CN 108160683 A CN108160683 A CN 108160683A CN 201810116172 A CN201810116172 A CN 201810116172A CN 108160683 A CN108160683 A CN 108160683A
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- Prior art keywords
- tin plating
- clad plate
- waste
- copper
- old
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000007747 plating Methods 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011889 copper foil Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 238000004070 electrodeposition Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- 230000005611 electricity Effects 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 13
- 238000003475 lamination Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 7
- 238000003801 milling Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 cupric Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a kind of method that waste and old tin plating copper-clad plate resource utilization utilizes.Include the following steps：The end of waste and old tin plating copper-clad plate is dipped into layering agent solution, immersion the tin plating of end is dipped to and covers copper and substrate de-lamination；The tin plating copper-clad plate impregnated is taken out, tin plating copper foil and substrate are obtained after carrying out mechanical stripping with the peeling machine of spool of tape；Copper foil and detin liquid are obtained after separation of solid and liquid is carried out after tin plating copper foil is leached detin with detin agent solution；Detin liquid is subjected to electrodeposition reaction, obtains metallic tin and electrodeposition waste liquid.The recycling to substrate, copper foil and metallic tin is realized respectively.There is industrial policy, the wide market that simple for process, equipment requirement is low, the technological element of a product and added value are high, is easy to industrialize, meet development national recycling economy.
Description
Technical field
The present invention relates to the coating technology field with metal material to material, more particularly to a kind of waste and old tin plating copper-clad plate
The method that utilizes of resource utilization.
Background technology
Copper-clad plate be it is a kind of by supporting material soak with resin or glass fibre, one or both sides are coated with copper foil, through hot pressing
Into a kind of board-like material.It is to make PCB（Printed wiring board）Basic material, be widely used in television set, computer, calculating
On the electronic products such as machine, mobile communication equipment and household electrical appliance.With the fast development of electronics technology, to raw material copper-clad plate
Demand sharp increase, lot-size production process produce about 20% leftover pieces, and about 1.2 hundred million ㎡ need to handle；Electronics produces
A large amount of waste and old tin plating copper-clad plates that the update of product is accelerated and generated, if long-term stack is not handled there are great environment with pacifying
Full hidden danger.On the other hand, the content of the precious metals such as cupric, tin of many waste and old copper-clad plates is up to 20 ~ 30%, significantly larger than one
As metal mine；And producing new resin substrate needs to expend a large amount of fossil feedstock.Therefore need to waste and old copper-clad plate into
Row resource utilization utilizes, and can be not only social creativity economic value, save mineral resources, expands employment, and can reduce
Harm to environment.With very high economy, environment and social value.
In the prior art, physics cracking and sorting, acidleach are mainly included to the method for waste and old tin plating copper-clad plate recycling
Deng.But the defects of existing and bias toward the recycling of metallic copper, having ignored the recycling of tin and resin substrate, and there are physics cracking and sortings
Gained copper particle contains more nonmetalloid, and acid solution immersion can then generate a large amount of waste water.Such as：
Chinese invention patent application（Application number：2016 1 0552992.8）Disclose a kind of " recycling of discarded copper-clad plate
Discarded copper-clad plate is broken into fragment by method ", this method, detaches metallic copper by waterpower shaking table and nonmetallic residue will be nonmetallic
Residue and resin and auxiliary agent blending and moulded board obtain artificial board, realize recycling to metallic copper and copper-clad plate is nonmetallic
Slag recovering processing is dalle.But this method exist it is relatively low to the rate of recovery of metallic copper, to the nonmetallic residual of copper-clad plate
The shortcomings of Slag treatment step is complicated.
Chinese utility model patent（The patent No.：ZL 2010 2 0690251.4）It provides " a kind of for copper foil of copper-clad plate
The milling device of recycling " carries out milling to the copper foil of copper-clad plate first, directly the copper foil milling in copper-clad plate is got off, milling
Main component is exactly copper foil material in the material to get off, and after milling is handled, and copper foil has formed tiny particulate matter,
Follow-up comminution process is also omitted in this way.The material that these millings are got off using physical treatment process separation copper product or is adopted
Copper product is extracted with metallurgy method.The patent exists biases toward the recycling of metallic copper, and the recycling for having ignored tin and resin substrate lacks
It falls into.
Chinese invention patent（The patent No.：2012 1 0017509.8）Providing one kind, " copper-clad plate removal process generates
The recovery method of copper-containing residue " first adds in dilute sulfuric acid to just waste residue is submerged, then by said mixture into copper-containing residue
Material filtering, filter residue are transferred in the reactive tank of band stirring, and the mixed acid solution that nitric acid and sulfuric acid form is added in into slot, under stirring after
Continue and add in suitable quantity of water into slot until submerging filter residue, when there is no stop reaction during bubble generation in reactive tank；Object after reaction
Material keeps settling at 60 DEG C~70 DEG C, filters, the heat preservation of gained filtrate；The filter residue being obtained by filtration reacts 1 time again with nitration mixture, merges two
Secondary filtrate, slow cooling are precipitated copper sulfate crystal to 15 DEG C~25 DEG C, centrifuge and obtain copper sulfate crystal.The patent makes
Copper-clad plate row is recycled, but there are problems that a large amount of waste water can be generated with nitration mixture.
Therefore, for of the prior art there are problem, it is urgent to provide a kind of comprehensive utilization of resources is efficient, technique is simple
Just, the method that the tin plating copper-clad plate resource utilization of high, the environmentally friendly type of metal recovery rate utilizes is to solve in the prior art
Shortcoming be particularly important.
Invention content
It is an object of the invention to avoid shortcoming of the prior art and provide a kind of comprehensive utilization of resources it is efficient,
Simple process, the method that utilizes of tin plating copper-clad plate resource utilization of high, the environmentally friendly type of metal recovery rate.
The purpose of the present invention is achieved through the following technical solutions, including step：
(1) end of waste and old tin plating copper-clad plate is dipped into layering agent solution and be soaked for a period of time, be dipped to the plating for impregnating end
Tin covers copper and substrate de-lamination；
(2) the tin plating copper-clad plate impregnated is taken out, tin plating copper foil and base is obtained after carrying out mechanical stripping with the peeling machine of spool of tape
Plate；
(3) copper foil and detin liquid are obtained after separation of solid and liquid is carried out after the tin plating copper foil being leached detin with detin agent solution；
(4) the detin liquid is subjected to electrodeposition reaction, obtains metallic tin and electrodeposition waste liquid.
It preferably,, can after the added a small amount of auxiliary agent circular regeneration of step (4) the electrodeposition waste liquid including step (5)
It is recycled as Tin-removal agent return to step (3).
Preferably, the step (1) layering agent used is by acetone, ethyl acetate, methyl acetate, potassium acetate, dimethyl
One or several kinds of mixed solutions in sulfoxide.
It is furthermore preferred that the end of the waste and old tin plating copper-clad plate of step (1) is dipped into the soaking depth in layering agent solution
For 1 ~ 20mm, soaking time is 1 ~ 10h.
Preferably, the Tin-removal agent used in the step (3) is one or several kinds of acid（HCl、H2SO4、HNO3) and salt
（CuSO4、Cu(NO3)2、CuCl2、SnCl4、SnSO4、Sn(NO3)2Mixed solution, sour a concentration of 20 ~ 100g/L, salt it is dense
It spends for 80 ~ 200g/L.
It is furthermore preferred that a concentration of 20 ~ 40g/L of acid.
It is another it is furthermore preferred that sour a concentration of 40 ~ 100g/L.
Preferably, using graphite as anode, stainless steel is cathode for step (4) the electrodeposition reaction, and the electric current of electrodeposition reaction is
50~200A/m2, voltage is 0.5 ~ 4V.
It is furthermore preferred that the pole span of the electrode is 50 ~ 200mm, preferred value 120mm.
It is furthermore preferred that electrolysis cycle speed is 10 ~ 40L/min.
Further, electrolysis cycle speed is 10 ~ 25L/min.
Another further, electrolysis cycle speed is 30 ~ 40L/min.
It is another it is furthermore preferred that in the step (4) auxiliary agent be Cu (OH)2Or Cu (OH)2CO3。
It is another it is furthermore preferred that：Auxiliary agent is SnCl in the step (4)2Or Sn (OH)2。
Above, the waste and old copper-clad plate of the step (1) includes leftover pieces, electronic apparatus that tin plating copper-clad plate produces and tears open
The old tin plating copper-clad plate unloaded down.
Beneficial effects of the present invention：
The waste and old tin plating copper-clad plate resource utilization of one kind of the present invention utilizes method, wherein, include the following steps：It will be waste and old tin plating
The end of copper-clad plate is dipped into layering agent solution, is dipped to immersion the tin plating of end and is covered copper and substrate de-lamination；The plating that will be impregnated
Tin copper-clad plate is taken out, and tin plating copper foil and substrate are obtained after carrying out mechanical stripping with the peeling machine of spool of tape；The tin plating copper foil is used
Copper foil and detin liquid are obtained after carrying out separation of solid and liquid after the leaching detin of detin agent solution；The detin liquid is subjected to electrodeposition reaction, is obtained
Metallic tin and electrodeposition waste liquid.
From there through being raw material by using waste and old tin plating copper-clad plate, under normal temperature and pressure conditions using Chemical Physics method into
Row full constituent resource utilization utilizes.It not only effectively eliminates environmental pollution that waste and old tin plating copper-clad plate stores up for a long time and safety is hidden
Suffer from, also solve the wasting of resources, secondary pollution problem existing for previous recycling copper-clad plate technology.The waste and old of the present invention tin plating covers copper
Plate resource utilization is had the characteristics that using method：
1. method technological process provided by the invention is short, raw material and by-product can recycle in process of production so that whole
A process realizes zero-emission, low energy consumption and economic and environment-friendly.
2. the present invention carries out full constituent recycling using chemicals logos to waste and old tin plating copper-clad plate, industry is realized
The high-valued comprehensive utilization of waste, the added value of the copper of recycling, tin and pdm substrate are high.
3. requirement of the present invention to energy consumption, equipment is low, convenient for industrialization promotion.
Description of the drawings
Using attached drawing, the invention will be further described, but the embodiment in attached drawing does not form any limit to the present invention
System.
Fig. 1 is the process flow diagram of the present invention.
Specific embodiment
The invention will be further described with the following Examples.
Embodiment 1
A kind of waste and old tin plating copper-clad plate resource utilization of the present invention is using one of embodiment of method, and such as Fig. 1 shows this realities
The content for applying metallic tin in copper-clad plate in example is 4%, and the content of copper is 18%, the content 78% of resin substrate.
A kind of method that utilizes of waste and old copper-clad plate resource utilization of the present invention, technological process as shown in Figure 1, including with
Lower step：
(1) agent solution containing layering is inserted into one end of copper-clad plate and carries out immersion 6h, soaking depth 10mm, be layered when impregnating end
After take out it is spare；
(2) peeling machine that the copper-clad plate being layered spool of tape occurs in step (1) one end removes substrate and copper foil, removes
Substrate afterwards can be recycled directly and be reused, and copper foil is spare.
(3) by step (2) copper foil according to liquid-solid ratio 5:1 is put into Tin-removal agent mixed solution, is leached under normal temperature and pressure conditions
4h, sour a concentration of 50g/L, a concentration of 100g/L of salt in Tin-removal agent carry out separation of solid and liquid and obtain pure copper foil and de- after detin
Tin liquor, copper foil directly recycle after washing, drying.
(4) it is anode in graphite by the detin liquid obtained by step (3), stainless steel is cathode, current density 100A/m2,
Progress electrodeposition 4h, the metallic tin that cathode plate obtains, electrodeposition devil liquor recovery are spare under conditions of voltage is 2V.
(5) the electrodeposition waste liquid obtained by step (4) is added into a small amount of auxiliary agent, and with the acid for adjusting pH value used in Tin-removal agent to 1 ~
It can be used for step (3) after 2 and carry out leaching detin use again；
After testing, the copper foil rate of recovery of copper-clad plate reaches 96%, and the rate of recovery of metallic tin is 95%, and purity reaches 98%, and substrate returns
Yield is 97%.
Embodiment 2
A kind of waste and old tin plating copper-clad plate resource utilization of the present invention utilizes one of embodiment of method, the master of the present embodiment 2
Want technical solution substantially the same manner as Example 1, the feature not laid down a definition in the present embodiment 2, using the explanation in embodiment 1,
It is no longer repeated herein.The present embodiment and embodiment 1 difference lies in：Step (3), by step (2) copper foil according to liquid-solid ratio
5:1 is put into Tin-removal agent mixed solution, leaches 5h under normal temperature and pressure conditions, sour a concentration of 30g/L, the concentration of salt in Tin-removal agent
For 80g/L, separation of solid and liquid is carried out after detin and obtains pure copper foil and detin liquid, copper foil directly recycles after washing, drying.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of range, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should manage
Solution, technical scheme of the present invention can be modified or replaced equivalently, without departing from technical solution of the present invention essence and
Range.
Claims (10)
1. a kind of method that waste and old tin plating copper-clad plate resource utilization utilizes, includes the following steps：
(1) end of waste and old tin plating copper-clad plate is dipped into layering agent solution, is dipped to immersion the tin plating of end and covers copper and substrate
Layering；
(2) the tin plating copper-clad plate impregnated is taken out, tin plating copper foil and base is obtained after carrying out mechanical stripping with the peeling machine of spool of tape
Plate；
(3) copper foil and detin liquid are obtained after separation of solid and liquid is carried out after the tin plating copper foil being leached detin with detin agent solution；
(4) the detin liquid is subjected to electrodeposition reaction, obtains metallic tin and electrodeposition waste liquid.
2. the method that a kind of waste and old tin plating copper-clad plate resource utilization according to claim 1 utilizes, it is characterised in that：It will
After the added a small amount of auxiliary agent circular regeneration of step (4) the electrodeposition waste liquid, Tin-removal agent return to step (3) can be used as to recycle.
3. the method that a kind of waste and old tin plating copper-clad plate resource utilization according to claim 1 or 2 utilizes, feature exist
In：The step (1) layering agent used is by in acetone, ethyl acetate, methyl acetate, potassium acetate, dimethyl sulfoxide (DMSO)
One or several kinds of mixed solutions.
4. the method that a kind of waste and old copper-clad plate resource utilization according to claim 3 utilizes, it is characterised in that：The step
Suddenly the end of (1) waste and old tin plating copper-clad plate is dipped into soaking depth in layering agent solution as 1 ~ 20mm, soaking time for 1 ~
10h。
5. the method that a kind of waste and old copper-clad plate resource utilization according to claim 1 or 2 utilizes, it is characterised in that：Institute
It is one or several kinds of acid to state the Tin-removal agent used in step (3)（HCl、H2SO4、HNO3) and salt（CuSO4、Cu(NO3)2、CuCl2、
SnCl4、SnSO4、Sn(NO3)2Mixed solution, sour a concentration of 20 ~ 100g/L, a concentration of 80 ~ 200g/L of salt.
6. the method that a kind of waste and old tin plating copper-clad plate resource utilization according to claim 1 or 2 utilizes, feature exist
In：Using graphite as anode, stainless steel is cathode for step (4) the electrodeposition reaction.
7. the method that a kind of waste and old tin plating copper-clad plate resource utilization according to claim 6 utilizes, it is characterised in that：Electricity
The electric current of product reaction is 50 ~ 200A/m2, voltage is 0.5 ~ 4V.
8. the method that a kind of waste and old tin plating copper-clad plate resource utilization according to claim 1 or 2 utilizes, feature exist
In：Auxiliary agent is Cu (OH) in the step (4)2Or Cu (OH)2CO3。
9. the method that a kind of waste and old tin plating copper-clad plate resource utilization according to claim 1 or 2 utilizes, feature exist
In：Auxiliary agent is SnCl in the step (4)2Or Sn (OH)2。
10. the method that a kind of waste and old tin plating copper-clad plate resource utilization according to claim 1 ~ 9 any one utilizes,
It is characterized in that：Leftover pieces, the electronic apparatus that the waste and old copper-clad plate of the step (1) includes tin plating copper-clad plate production disassemble
Old tin plating copper-clad plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810116172.3A CN108160683A (en) | 2018-02-06 | 2018-02-06 | A kind of method that waste and old tin plating copper-clad plate resource utilization utilizes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825716A (en) * | 2019-03-28 | 2019-05-31 | 湖南科技大学 | A method of recycling copper and tin in waste and old tin plating copper-clad plate |
| CN110434159A (en) * | 2019-08-26 | 2019-11-12 | 华南理工大学 | A method of quickly recycling copper foil in waste and old copper-clad plate |
| RU2795912C1 (en) * | 2022-07-11 | 2023-05-15 | Аркадий Нахимович Фейгельман | Method for processing tin-plated copper waste |
| CN116804276A (en) * | 2022-11-22 | 2023-09-26 | 天地人和(南通)环保科技有限公司 | Environment-friendly recyclable tin stripping liquid for tinned copper and tin recovery process |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003112141A (en) * | 2001-10-02 | 2003-04-15 | Mitsubishi Heavy Ind Ltd | Treatment system for coating material containing hazardous substance |
| CN101121289A (en) * | 2007-09-21 | 2008-02-13 | 北京工业大学 | Method for recovering and treating waste flexible circuit board |
| CN101269378A (en) * | 2008-04-23 | 2008-09-24 | 北京正康创智科技发展有限公司 | Method for separating fiberglass cloth and sheet metal in waste printed circuit board |
| WO2009145833A2 (en) * | 2008-04-02 | 2009-12-03 | Fengchun Xie | Ultrasound assisted heavy metal recovery |
| CN103741142A (en) * | 2014-01-10 | 2014-04-23 | 中南大学 | Method for recycling tin from waste tin-stripping solution based on tin-stripping solution of hydrochloric acid-tin salt system |
| CN103894391A (en) * | 2014-03-27 | 2014-07-02 | 宁波同道恒信环保科技有限公司 | Layered peeling method of circuit board |
| CN105112674A (en) * | 2015-09-18 | 2015-12-02 | 中南大学 | All-wet recovery process for waste circuit boards |
| CN106381390A (en) * | 2016-09-14 | 2017-02-08 | 南昌大学 | Waste LED lighting bulb recycling method |
| CN106978536A (en) * | 2017-03-30 | 2017-07-25 | 桑德（天津）再生资源投资控股有限公司 | The method for splitting waste and old circuit board |
-
2018
- 2018-02-06 CN CN201810116172.3A patent/CN108160683A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003112141A (en) * | 2001-10-02 | 2003-04-15 | Mitsubishi Heavy Ind Ltd | Treatment system for coating material containing hazardous substance |
| CN101121289A (en) * | 2007-09-21 | 2008-02-13 | 北京工业大学 | Method for recovering and treating waste flexible circuit board |
| WO2009145833A2 (en) * | 2008-04-02 | 2009-12-03 | Fengchun Xie | Ultrasound assisted heavy metal recovery |
| CN101269378A (en) * | 2008-04-23 | 2008-09-24 | 北京正康创智科技发展有限公司 | Method for separating fiberglass cloth and sheet metal in waste printed circuit board |
| CN103741142A (en) * | 2014-01-10 | 2014-04-23 | 中南大学 | Method for recycling tin from waste tin-stripping solution based on tin-stripping solution of hydrochloric acid-tin salt system |
| CN103894391A (en) * | 2014-03-27 | 2014-07-02 | 宁波同道恒信环保科技有限公司 | Layered peeling method of circuit board |
| CN105112674A (en) * | 2015-09-18 | 2015-12-02 | 中南大学 | All-wet recovery process for waste circuit boards |
| CN106381390A (en) * | 2016-09-14 | 2017-02-08 | 南昌大学 | Waste LED lighting bulb recycling method |
| CN106978536A (en) * | 2017-03-30 | 2017-07-25 | 桑德（天津）再生资源投资控股有限公司 | The method for splitting waste and old circuit board |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825716A (en) * | 2019-03-28 | 2019-05-31 | 湖南科技大学 | A method of recycling copper and tin in waste and old tin plating copper-clad plate |
| CN110434159A (en) * | 2019-08-26 | 2019-11-12 | 华南理工大学 | A method of quickly recycling copper foil in waste and old copper-clad plate |
| RU2795912C1 (en) * | 2022-07-11 | 2023-05-15 | Аркадий Нахимович Фейгельман | Method for processing tin-plated copper waste |
| CN116804276A (en) * | 2022-11-22 | 2023-09-26 | 天地人和(南通)环保科技有限公司 | Environment-friendly recyclable tin stripping liquid for tinned copper and tin recovery process |
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