CN114317978A - Method for recovering micro-nano copper powder from waste printed circuit board - Google Patents
Method for recovering micro-nano copper powder from waste printed circuit board Download PDFInfo
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- CN114317978A CN114317978A CN202111632124.8A CN202111632124A CN114317978A CN 114317978 A CN114317978 A CN 114317978A CN 202111632124 A CN202111632124 A CN 202111632124A CN 114317978 A CN114317978 A CN 114317978A
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- copper powder
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 147
- 239000010949 copper Substances 0.000 claims abstract description 106
- 229910052802 copper Inorganic materials 0.000 claims abstract description 100
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 238000002386 leaching Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000007885 magnetic separation Methods 0.000 claims abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000005484 gravity Effects 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000002572 peristaltic effect Effects 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 239000012634 fragment Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 230000005294 ferromagnetic effect Effects 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- -1 and finally Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 7
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- 239000000428 dust Substances 0.000 abstract description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010793 electronic waste Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
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- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recovering micro-nano copper powder from a waste printed circuit board, which specifically comprises the following steps: crushing the waste printed circuit board; grinding the waste printed circuit board; mixing and stirring the slurry; screening by using gravity; separating heavy products by magnetic separation; oxidation reaction of copper-rich aggregate; separating and drying the copper leaching solution; electrolyzing the copper metal mixture; passivating copper powder; and (4) collecting the nano copper powder. The process of the invention adopts a mechanical and chemical sorting method, utilizes the difference of material density to carry out resource recovery, and avoids secondary pollution generated by a chemical method; by adopting the table sorting method, not only can the generation of dust be avoided, but also the sorting water can be recycled, thus realizing the pollution-free whole sorting process; the method can realize recycling of micro-fine particle materials by sorting through a shaking table, has the advantages of wide sorting level, small environmental pollution and the like, and has wide applicability.
Description
Technical Field
The invention belongs to the technical field of electronic waste recycling, and particularly relates to a method for recycling micro-nano copper powder from a waste printed circuit board.
Background
In recent years, as society has progressed, the amount of electronic waste is increasing at an alarming rate. Waste Printed Circuit Boards (WPCBs) are mainly composed of resin, glass fiber, kraft paper, and high-purity copper foil, and have dual attributes of harm and resources. Not only contains a large amount of toxic and harmful chemical substances, such as toxic metals like Pb, Hg, Cr and the like and organic substances like brominated flame retardants; and also contains valuable metals such as Cu, Fe, Al and the like and rare and precious metals such as Ag, Au, Pd and the like, thereby having higher resource recovery value. The copper content is higher and can be 20-40 times of that of copper ore.
Printed wiring boards, which are important components of electronic products, are present in almost all electronic devices, and therefore, a rapid increase in the amount of electronic waste is indicative of a rapid increase in the amount of waste printed wiring boards. The metal content in the printed circuit board accounts for about 40%, wherein the main valuable metal is nonferrous metal, and the content of various elements such as copper, tin, gold, silver and the like in the printed circuit board is higher than that in the currently mined ore. Therefore, the waste printed circuit board has high recycling value.
Mature methods for recovering copper from WPCBs at home and abroad are roughly divided into a mechanical physical method, a fire method and a wet method. At present, WPCBs are crushed by a mechanical-physical method, and are separated according to the physical characteristics of materials, so that a mixture of metal concentrates and nonmetal is generally obtained, and the Cu content is about 60%. Although the pollution is small and the recovery rate is high, pure Cu cannot be obtained. The fire metallurgy method directly adds WPCBs into a fluidized bed incinerator for incineration to obtain a product copper ingot, but pollution such as dioxin can be generated. The wet metallurgy is to contact WPCBs with water solution or other liquid, to convert Cu in the raw material into liquid phase through chemical reaction, etc., to remove impurities, to enrich copper, and to recover copper in the form of simple compound. In order to obtain pure Cu, the general hydrometallurgy comprises units such as leaching, liquid-solid separation, solution purification, metal extraction in solution and the like, and the steps are various.
Leaching Cu in hydrometallurgy involves both acidic and alkaline leaching. Alkaline leaching mainly means that metal compounds such as oxides or carbonic acid compounds of metal ions, such as Cu, Zn, Ag, Ni and the like are directly dissolved by utilizing the principle that the metal ions and ammonia form complexes. Compared with the acid method, the leached metal is more selective, and metals such as Fe, Al and the like can generate insoluble substances under the weak alkaline condition under the condition that the metals are easily dissolved under the acidic condition, so that the metals cannot be leached.
The invention discloses a method for recovering copper from waste printed circuit boards, which is called CN112921356A and is invented and created by taking an alkaline system as electrolyte, adopting an ore pulp electrolysis method, and simultaneously carrying out leaching and electrodeposition of Cu, thereby recovering copper from the waste printed circuit boards and obtaining copper products such as copper foil or copper powder.
However, the existing method for recovering copper powder from waste printed circuit boards has the problems of complex production process and low recovery efficiency of copper due to the fact that physical extraction and chemical extraction cannot be effectively combined.
Therefore, the invention is very necessary to invent a method for recovering micro-nano copper powder from waste printed circuit boards.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for recovering micro-nano copper powder from a waste printed circuit board, which aims to solve the problems that the existing method for recovering copper powder from the waste printed circuit board is complex in production process, and the recovery efficiency of copper is low due to the fact that physical extraction and chemical extraction cannot be effectively combined.
The method for recovering the micro-nano copper powder from the waste printed circuit board specifically comprises the following steps:
the method comprises the following steps: crushing the waste printed circuit board;
step two: grinding the waste printed circuit board;
step three: mixing and stirring the slurry;
step four: screening by using gravity;
step five: separating heavy products by magnetic separation;
step six: oxidation reaction of copper-rich aggregate;
step seven: separating and drying the copper leaching solution;
step eight: electrolyzing the copper metal mixture;
step nine: passivating copper powder;
step ten: and (4) collecting the nano copper powder.
Preferably, in the step one, the waste printed circuit board is coarsely crushed into fragments smaller than 15cm × 15cm by the crusher, and then the fragments are crushed by a powerful plastic crusher and a sealed sample preparation crusher to obtain waste printed circuit board crushed materials, wherein the particle size of the waste printed circuit board crushed materials is less than or equal to 30 meshes.
Preferably, in the second step, the small pieces of materials obtained by the preliminary shearing in the first step are sent to a cutting grinder, and in the cutting grinder, the small pieces of materials are further crushed by a blade rotating at high speed to obtain fine-grained materials with the granularity of less than 10 mm.
Preferably, in the third step, the fine-grained materials in the second step and a proper amount of water are fed into a stirring tank together for stirring, so that the fine-grained materials are fully dispersed in the water, and finally, slurry with the solid content of 20% -35% is obtained.
Preferably, in the fourth step, the slurry in the third step is sorted by a shaker to separate the material into a heavy product and a light product, and the light product obtained at this time is a final light product, and the main component of the light product is plastic; the heavy product to be obtained is a metal mixture.
Preferably, in the fifth step, the metal mixture in the fourth step is sent to a magnetic separation device, ferromagnetic substances are separated, and the rest is copper-rich aggregate of nonferrous metals such as copper, lead, zinc, tin, nickel and the like.
Preferably, in the sixth step, the copper-rich aggregate obtained in the fifth step is soaked in ammonia water, hydrogen peroxide is dropwise added into the leaching solution at room temperature under the stirring condition of an electromagnetic stirrer, the reaction time is controlled to be 2-4 hours, after the reaction is finished, the waste is taken out, solid-liquid separation is carried out, the obtained filtrate is the copper-containing leaching solution, nascent oxygen generated in the oxidation process has strong oxidizability, and copper is oxidized to obtain copper oxide.
Preferably, in the sixth step, the mass ratio of the copper-rich aggregate to the hydrogen peroxide to the ammonia water is 1 to (0.2-1.2) to (6-12); the molar concentration of the ammonia water is 4-16 mol/L; the mass percentage concentration of the hydrogen peroxide is 30-45%.
Preferably, in the sixth step, the hydrogen peroxide is an oxidant, and the nascent oxygen generated in the oxidation process has strong oxidizing property, so that copper is oxidized to obtain copper oxide.
Preferably, in the seventh step, the obtained copper leaching solution is placed into a reaction container of a spray dryer, a peristaltic pump is used for driving a pipette to absorb the copper-containing leaching solution, the copper-containing leaching solution is subjected to a spray drying process, the copper-containing leaching solution is prepared by adopting a spray drying method, the temperature of an air inlet of the spray dryer is 80-120 ℃, the rotation speed of the peristaltic pump is 80-100 r/min, and the air output of a high-pressure gas flow meter is 8-32 l/min; thereby obtaining a copper metal mixture.
Preferably, in the eighth step, the copper metal mixture dried in the seventh step and the copper oxide in the sixth step are added into an anode chamber of the electrolytic cell, and a proper amount of CuSO is added4·5H2O, NaCl, concentrated H2SO4Preparing electrolyte with ionic liquid, adding strong oxidizing substance, connecting power supply, using copper metal mixture and ruthenium-plated titanium plate as cathode and anode respectively, setting current density at 50-100 mA/cm2Electrolyzing for 2-8 h; magnetic stirring is adopted in the electrolysis process.
Preferably, in the ninth step, after the electrolytic reaction in the eighth step is completed, copper powder deposited in the cathode chamber of the copper metal mixture is collected and placed in the benzotriazole solution for passivation.
Preferably, in the step ten, the passivated copper powder is placed into a muffle furnace again for calcination treatment, the temperature is controlled to be 500-600 ℃, the time is 0.5-1 hour, and then the copper powder is cooled to room temperature along with the muffle furnace, so that the nano-copper powder is finally obtained; or centrifuging after ultrasonic treatment, and collecting nano-copper powder after vacuum drying, wherein the particle size of the nano-copper powder is 0.5-1.0 micron.
Compared with the prior art, the invention has the following beneficial effects: metal impurities and non-metal impurities in the crushed waste printed circuit boards are separated by a physical mechanical method, and other metal and non-metal materials can be recycled;
the process of the invention adopts a mechanical and chemical sorting method, utilizes the difference of material density to carry out resource recovery, and avoids secondary pollution generated by a chemical method; by adopting the table sorting method, not only can the generation of dust be avoided, but also the sorting water can be recycled, thus realizing the pollution-free whole sorting process; the method has the advantages that the recycling of the micro-fine particle materials can be realized through the sorting by the table concentrator, the sorting level is wide, the environmental pollution is low, and the like, and the method has wide applicability;
the preparation process greatly shortens the reaction time, reduces the energy consumption, obtains the copper product, is a green and efficient technology, has low operation cost, simple recovery process, no secondary pollution and high economic value.
Drawings
FIG. 1 is a flow chart of a method for recovering micro-nano copper powder from waste printed circuit boards.
Fig. 2 is a modified partial front view of a crusher to which the present invention is applied.
Fig. 3 is a modified partial rear view of a crusher to which the present invention is applied.
Fig. 4 shows the structure of the nano-copper powder brush plate of the centrifugal dryer applied in the invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
as shown in figure 1
The method for recovering the micro-nano copper powder from the waste printed circuit board specifically comprises the following steps:
the method comprises the following steps: crushing the waste printed circuit board;
step two: grinding the waste printed circuit board;
step three: mixing and stirring the slurry;
step four: screening by using gravity;
step five: separating heavy products by magnetic separation;
step six: oxidation reaction of copper-rich aggregate;
step seven: separating and drying the copper leaching solution;
step eight: electrolyzing the copper metal mixture;
step nine: passivating copper powder;
step ten: and (4) collecting the nano copper powder.
In the above embodiment, specifically, in the step one, the waste printed circuit board is coarsely crushed into pieces smaller than 15cm × 15cm by the crusher, and then the pieces are crushed by the powerful plastic crusher and the sealed sample preparation crusher to obtain crushed waste printed circuit board materials, wherein the particle size of the crushed waste printed circuit board materials is less than or equal to 30 meshes.
In the above embodiment, specifically, in the second step, the small pieces of material obtained by the preliminary shearing in the first step are sent to a cutting grinder, and in the cutting grinder, the small pieces of material are further crushed by a blade rotating at a high speed to obtain fine-grained material with a grain size of less than 10 mm.
In the above embodiment, specifically, in the third step, the fine-grained material in the second step and a proper amount of water are fed into a stirring tank together for stirring, so that the fine-grained material is fully dispersed in the water, and finally, slurry with a solid content of 20% to 35% is obtained.
In the above embodiment, specifically, in the fourth step, the slurry in the third step is separated by a shaker to separate the material into a heavy product and a light product, and the light product obtained at this time is the final light product, and the main component of the light product is plastic; the heavy product to be obtained is a metal mixture.
In the above embodiment, specifically, in the fifth step, the metal mixture in the fourth step is sent to a magnetic separation device to separate ferromagnetic substances, and the rest is copper-rich aggregate of nonferrous metals such as copper, lead, zinc, tin, nickel, and the like.
In the above embodiment, specifically, in the sixth step, the copper-rich aggregate obtained in the fifth step is soaked in ammonia water, hydrogen peroxide is dropwise added into the leaching solution at room temperature under the stirring condition of an electromagnetic stirrer, the reaction time is controlled to be 2-4 hours, after the reaction is finished, the waste is taken out, solid-liquid separation is performed, the obtained filtrate is a copper-containing leaching solution, nascent oxygen generated in the oxidation process has strong oxidizing property, and copper is oxidized to obtain copper oxide.
In the above embodiment, specifically, in the sixth step, the mass ratio of the copper-rich aggregate, the hydrogen peroxide and the ammonia water is 1: 0.2-1.2: 6-12; the molar concentration of the ammonia water is 4-16 mol/L; the mass percentage concentration of the hydrogen peroxide is 30-45%.
In the above embodiment, specifically, in the sixth step, the hydrogen peroxide is an oxidant, and the nascent oxygen generated in the oxidation process has strong oxidizing property, so that copper is oxidized to obtain copper oxide.
In the above embodiment, specifically, in the seventh step, the obtained copper leaching solution in the sixth step is placed in a reaction vessel of a spray dryer, a peristaltic pump is used to drive a pipette to absorb the copper-containing leaching solution, and the copper-containing leaching solution is subjected to a spray drying process, wherein the copper-containing leaching solution is prepared by the spray drying process, and the spray dryer has an air inlet temperature of 80-120 ℃, a rotation speed of 80-100 rpm of the peristaltic pump, and an air outlet volume of a high-pressure gas flow meter of 8-32 l/min; thereby obtaining a copper metal mixture.
In the above embodiment, specifically, in the step eight, the copper metal mixture dried in the step seven and the copper oxide in the step six are added into the anode chamber of the electrolytic cell, and an appropriate amount of CuSO is added4·5H2O, NaCl, concentrated H2SO4Preparing electrolyte with ionic liquid, adding strong oxidizing substance, connecting power supply, using copper metal mixture and ruthenium-plated titanium plate as cathode and anode respectively, setting current density at 50-100 mA/cm2Electrolyzing for 2-8 h; magnetic stirring is adopted in the electrolysis process.
In the above embodiment, specifically, in the ninth step, the copper powder deposited in the cathode chamber of the copper metal mixture after the electrolytic reaction in the eighth step is completed is collected and placed in the benzotriazole solution for passivation.
In the above embodiment, specifically, in the step ten, the passivated copper powder is placed into the muffle furnace again for calcination treatment, the temperature is controlled to be 500-600 ℃, the time is 0.5-1 hour, and then the copper powder is cooled to room temperature along with the muffle furnace, so as to obtain the nano-copper powder finally; or centrifuging after ultrasonic treatment, and collecting nano-copper powder after vacuum drying, wherein the particle size of the nano-copper powder is 0.5-1.0 micron.
As shown in figures 2 and 3
In order to match the method for recovering micro-nano copper powder from the waste printed circuit board, mechanical equipment of a screening crusher 1 is improved, a crushing cutter roll 2 is embedded in the middle position inside the screening crusher 1, a magnetic separation shaft 3 is embedded in the lower side inside the screening crusher 1, a cleaning push ring 4 is sleeved on the outer surface of the magnetic separation shaft 3, the upper part and the lower part of the right side of the cleaning push ring 4 are respectively connected with a connecting lug plate 5 through screws, the right side of the screening crusher 1 is connected with a cylinder rod 6 through a screw, the output end of the cylinder rod 6 is connected with an extension rod 7 through a bolt, and the top end of the extension rod 7 is connected to the rear part of the connecting lug plate 5 through a screw; a ferromagnetic substance outlet 8 is embedded in the left side of the screening grinder 1, and a copper-rich collective outlet 9 of nonferrous metals is arranged on the lower side of the front part of the screening grinder 1;
the rear part of the screening and crushing machine 1 is in screwed connection with a plastic light product collecting cover 10 and a suction fan 11, the output end of the suction fan 11 is in screwed connection with a guide pipe 12, and the lower part of the guide pipe 12 is tied with a collecting bag 13.
As shown in figure 4
In order to match the method for recovering micro-nano copper powder from the waste printed circuit board, the centrifugal dryer mechanical equipment is improved, a nano copper powder brush plate structure is added, the nano copper powder brush plate structure comprises a lifting air pressure rod 21, a rotating motor 22, a rotating shaft 23, a connecting cap 24, a connecting lug plate 25, an extension plate 26 and a cleaning brush 27, the rotating motor 22 is connected to the lower portion of the lifting air pressure rod 21 through bolts, the rotating shaft 23 is connected to the output end of the rotating motor 22 through a coupler, the connecting cap 24 is connected to the lower end of the rotating shaft 23 through bolts, the connecting lug plates 25 are respectively welded to two sides of the connecting cap 24, the extension plate 26 is connected to the rear portion of the connecting lug plate 25 through bolts, and the cleaning brush 27 is connected to the top end of the outer side of the extension plate 26 through bolts.
Example 1
The invention discloses a method for recovering micro-nano copper powder from a waste printed circuit board, which comprises the following steps:
the method comprises the following steps: crushing the waste printed circuit board; coarsely crushing the waste printed circuit board into fragments smaller than 15cm multiplied by 15cm by using a crusher, and crushing the fragments by using a powerful plastic crusher and a sealed sample preparation crusher to obtain crushed waste printed circuit board materials, wherein the particle size of the crushed waste printed circuit board materials is less than or equal to 30 meshes;
step two: grinding the waste printed circuit board; feeding the small materials obtained by the preliminary shearing in the step one into a cutting grinder, and further crushing the small materials by a high-speed rotating blade in the cutting grinder to obtain fine-grained materials with the granularity of less than 10 mm;
step three: mixing and stirring the slurry; feeding the fine-grained materials in the step two and a proper amount of water into a stirring tank together for stirring, so that the fine-grained materials are fully dispersed in the water, and finally obtaining slurry with the solid content of 20%;
step four: screening by using gravity; separating the slurry in the third step into a heavy product and a light product by a table concentrator, wherein the light product is the final light product and the main component of the light product is plastic; the heavy product obtained is a metal mixture;
step five: separating heavy products by magnetic separation; feeding the metal mixture obtained in the fourth step into magnetic separation equipment, and separating out ferromagnetic substances, wherein the rest is copper-rich aggregate of nonferrous metals such as copper, lead, zinc, tin, nickel and the like;
step six: oxidation reaction of copper-rich aggregate; soaking the copper-rich aggregate obtained in the fifth step in ammonia water, dropwise adding hydrogen peroxide into the leaching solution at room temperature under the stirring condition of an electromagnetic stirrer, controlling the reaction time to be 2 hours, taking out the waste material after the reaction is finished, and carrying out solid-liquid separation to obtain filtrate, namely the copper-containing leaching solution; the mass ratio of the copper-rich aggregate, the hydrogen peroxide and the ammonia water is 1: 0.2: 6; the molar concentration of the ammonia water is 4-16 mol/L; the mass percentage concentration of the hydrogen peroxide is 30 percent;
step seven: separating and drying the copper leaching solution; putting the obtained copper leaching solution into a reaction container of a spray dryer, sucking the copper-containing leaching solution by adopting a mode of driving a pipette by a peristaltic pump, and carrying out a spray drying process on the copper-containing leaching solution, wherein the copper-containing leaching solution is prepared by adopting the spray drying method, the temperature of an air inlet of the spray dryer is 80 ℃, the rotation speed of the peristaltic pump is 80 revolutions per minute, and the gas output of a high-pressure gas flowmeter is 8 liters per minute; thereby obtaining a copper metal mixture;
step eight: electrolyzing the copper metal mixture; adding the copper metal mixture dried in the step seven and the copper oxide in the step six into an anode chamber of an electrolytic cell, and adding a proper amount of CuSO4·5H2O, NaCl, concentrated H2SO4Preparing electrolyte with ionic liquid, adding strong oxidizing substance, turning on power supply, using copper metal mixture and ruthenium-plated titanium plate as cathode and anode respectively, and setting current density at 50mA/cm2Electrolyzing for 2 hours; magnetic stirring is adopted in the electrolysis process;
step nine: passivating copper powder; collecting copper powder deposited in the cathode chamber of the copper metal mixture after the electrolytic reaction in the step eight is finished, and placing the copper powder in a benzotriazole solution for passivation;
step ten: collecting the nanometer copper powder; placing the passivated copper powder into a muffle furnace again for calcination treatment, controlling the temperature at 50 ℃ for 0.5 hour, and then cooling to room temperature along with the muffle furnace to finally obtain nano copper powder; or centrifuging after ultrasonic treatment, and collecting nano-copper powder after vacuum drying, wherein the particle size of the nano-copper powder is 0.5-1.0 micron.
Example 2
The invention discloses a method for recovering micro-nano copper powder from a waste printed circuit board, which comprises the following steps:
the method comprises the following steps: crushing the waste printed circuit board; coarsely crushing the waste printed circuit board into fragments smaller than 15cm multiplied by 15cm by using a crusher, and crushing the fragments by using a powerful plastic crusher and a sealed sample preparation crusher to obtain crushed waste printed circuit board materials, wherein the particle size of the crushed waste printed circuit board materials is less than or equal to 30 meshes;
step two: grinding the waste printed circuit board; feeding the small materials obtained by the preliminary shearing in the step one into a cutting grinder, and further crushing the small materials by a high-speed rotating blade in the cutting grinder to obtain fine-grained materials with the granularity of less than 10 mm;
step three: mixing and stirring the slurry; feeding the fine-grained materials in the step two and a proper amount of water into a stirring tank together for stirring, so that the fine-grained materials are fully dispersed in the water, and finally obtaining slurry with the solid content of 35%;
step four: screening by using gravity; separating the slurry in the third step into a heavy product and a light product by a table concentrator, wherein the light product is the final light product and the main component of the light product is plastic; the heavy product obtained is a metal mixture;
step five: separating heavy products by magnetic separation; feeding the metal mixture obtained in the fourth step into magnetic separation equipment, and separating out ferromagnetic substances, wherein the rest is copper-rich aggregate of nonferrous metals such as copper, lead, zinc, tin, nickel and the like;
step six: oxidation reaction of copper-rich aggregate; soaking the copper-rich aggregate obtained in the fifth step in ammonia water, dropwise adding hydrogen peroxide into the leaching solution at room temperature under the stirring condition of an electromagnetic stirrer, controlling the reaction time to be 2-4 hours, taking out the waste after the reaction is finished, and carrying out solid-liquid separation to obtain filtrate, namely the copper-containing leaching solution; the mass ratio of the copper-rich aggregate, the hydrogen peroxide and the ammonia water is 1: 1.2: 12; the molar concentration of the ammonia water is 4-16 mol/L; the mass percentage concentration of the hydrogen peroxide is 45%;
step seven: separating and drying the copper leaching solution; putting the obtained copper leaching solution into a reaction container of a spray dryer, sucking the copper-containing leaching solution by adopting a mode of driving a pipette by a peristaltic pump, and carrying out a spray drying process on the copper-containing leaching solution, wherein the copper-containing leaching solution is prepared by adopting the spray drying method, the temperature of an air inlet of the spray dryer is 120 ℃, the rotation speed of the peristaltic pump is 100 revolutions per minute, and the gas output of a high-pressure gas flowmeter is 32 liters per minute; thereby obtaining a copper metal mixture;
step eight: copper metal mixtureElectrolysis of (2); adding the copper metal mixture dried in the step seven and the copper oxide in the step six into an anode chamber of an electrolytic cell, and adding a proper amount of CuSO4·5H2O, NaCl, concentrated H2SO4Preparing electrolyte with ionic liquid, adding strong oxidizing substance, connecting power supply, using copper metal mixture and ruthenium-plated titanium plate as cathode and anode, respectively, setting current density at 100mA/cm2Electrolyzing for 8 hours; magnetic stirring is adopted in the electrolysis process;
step nine: passivating copper powder; collecting copper powder deposited in the cathode chamber of the copper metal mixture after the electrolytic reaction in the step eight is finished, and placing the copper powder in a benzotriazole solution for passivation;
step ten: collecting the nanometer copper powder; placing the passivated copper powder into a muffle furnace again for calcination treatment, controlling the temperature at 600 ℃ for 1 hour, and then cooling to room temperature along with the muffle furnace to finally obtain nano-copper powder; or centrifuging after ultrasonic treatment, and collecting nano-copper powder after vacuum drying, wherein the particle size of the nano-copper powder is 0.5-1.0 micron.
The technical solutions of the present invention or similar technical solutions designed by those skilled in the art based on the teachings of the technical solutions of the present invention are all within the scope of the present invention.
Claims (10)
1. A method for recovering micro-nano copper powder from a waste printed circuit board is characterized by comprising the following steps:
the method comprises the following steps: crushing the waste printed circuit board;
step two: grinding the waste printed circuit board;
step three: mixing and stirring the slurry;
step four: screening by using gravity;
step five: separating heavy products by magnetic separation;
step six: oxidation reaction of copper-rich aggregate;
step seven: separating and drying the copper leaching solution;
step eight: electrolyzing the copper metal mixture;
step nine: passivating copper powder;
step ten: and (4) collecting the nano copper powder.
2. The method for recovering the micro-nano copper powder from the waste printed circuit board as claimed in claim 1, wherein in the step one, the waste printed circuit board is coarsely crushed into fragments smaller than 15cm x 15cm by using the crusher, and then the fragments are crushed by using a powerful plastic crusher and a sealed sample crusher to obtain the crushed waste printed circuit board, wherein the particle size of the crushed waste printed circuit board is less than or equal to 30 meshes.
3. The method for recovering the micro-nano copper powder from the waste printed circuit board as claimed in claim 1, wherein in the second step, the small pieces of material obtained by the primary shearing in the first step are sent to a cutting grinder, and in the cutting grinder, the small pieces of material are further crushed by a blade rotating at a high speed to obtain fine-grained material with the granularity of less than 10 mm.
4. The method for recovering the micro-nano copper powder from the waste printed circuit board as claimed in claim 1, wherein in the third step, the fine material in the second step and a proper amount of water are fed into a stirring tank together for stirring, so that the fine material is fully dispersed in the water, and finally, slurry with the solid content of 20-35% is obtained.
5. The method for recovering the micro-nano copper powder from the waste printed circuit board and the preparation method thereof as claimed in claim 1, wherein in the fourth step, the slurry in the third step is separated into a heavy product and a light product by shaking table separation, and the light product obtained at this time is a final light product, and the main component of the light product is plastic; the heavy product to be obtained is a metal mixture.
6. The method for recovering the micro-nano copper powder from the waste printed circuit board as claimed in claim 1, wherein in the fifth step, the metal mixture in the fourth step is sent to a magnetic separation device to separate ferromagnetic substances, and the rest is copper-rich aggregate of nonferrous metals such as copper, lead, zinc, tin and nickel.
7. The method for recovering the micro-nano copper powder from the waste printed circuit board according to claim 1, wherein in the sixth step, the copper-rich aggregate obtained in the fifth step is soaked in ammonia water, hydrogen peroxide is dropwise added into the leaching solution at room temperature under the stirring condition of an electromagnetic stirrer, the reaction time is controlled to be 2-4 hours, after the reaction is finished, the waste is taken out, solid-liquid separation is carried out, the obtained filtrate is the copper-containing leaching solution, and nascent oxygen generated in the oxidation process has strong oxidizing property, so that copper is oxidized to obtain copper oxide.
8. The method for recovering the micro-nano copper powder from the waste printed circuit board according to claim 1, wherein in the sixth step, the mass ratio of the copper-rich aggregate, the hydrogen peroxide and the ammonia water is 1: 0.2-1.2: 6-12; the molar concentration of the ammonia water is 4-16 mol/L; the mass percentage concentration of the hydrogen peroxide is 30-45%.
9. The method for recovering the micro-nano copper powder from the waste printed circuit board according to claim 1, wherein in the seventh step, the obtained copper leaching solution in the sixth step is placed into a reaction container of a spray dryer, a peristaltic pump is used for driving a pipette to suck the copper-containing leaching solution and perform a spray drying process on the copper-containing leaching solution, the spray drying process is adopted for preparation, the temperature of an air inlet of the spray dryer is 80-120 ℃, the rotation speed of the peristaltic pump is 80-100 r/min, and the air output of a high-pressure gas flowmeter is 8-32 l/min; thereby obtaining a copper metal mixture.
10. The method for recovering the micro-nano copper powder from the waste printed circuit board according to claim 1, wherein in the step ten, the passivated copper powder is placed into a muffle furnace again for calcination treatment, the temperature is controlled to be 500-600 ℃, the time is 0.5-1 hour, and then the passivated copper powder is cooled to room temperature along with the muffle furnace, so that the nano copper powder is finally obtained; or centrifuging after ultrasonic treatment, and collecting nano-copper powder after vacuum drying, wherein the particle size of the nano-copper powder is 0.5-1.0 micron.
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