CN112143893B - Method for wet separation and copper recovery of waste enameled wire - Google Patents
Method for wet separation and copper recovery of waste enameled wire Download PDFInfo
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- CN112143893B CN112143893B CN201910578388.6A CN201910578388A CN112143893B CN 112143893 B CN112143893 B CN 112143893B CN 201910578388 A CN201910578388 A CN 201910578388A CN 112143893 B CN112143893 B CN 112143893B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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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
Abstract
The invention provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps: preparing the waste enameled wires into copper rice through pretreatment; mixing the copper rice and a reducing solution to form a mixture, and then grinding the mixture by a wet method to obtain grinding slurry; performing cyclone separation on the obtained ground slurry to obtain a bottom flow and overflow mixture; and performing solid-liquid separation on the obtained bottom flow to obtain purified copper rice and bottom flow filtrate, and performing solid-liquid separation on the overflow mixture to obtain waste paint and overflow filtrate. According to the invention, the copper in the waste enameled wire is separated from the insulating paint by combining wet grinding and cyclone separation, and the reducing solution is added in the wet grinding process, so that the recovery rate of the copper in the waste enameled wire is ensured. The purity of copper in the copper product obtained by recovery can reach 99.0 wt%, and the recovery rate of copper in the waste enameled wire can reach 98.8%.
Description
Technical Field
The invention belongs to the technical field of environmental protection, relates to a method for recycling waste enameled wires, and particularly relates to a method for wet separation and copper recovery of waste enameled wires.
Background
Enameled wires are the main raw materials of products such as motors, electric appliances and household appliances, and particularly the electric power industry has been continuously and rapidly increased in recent years. The rapid development of household appliances brings a wide field for the application of enameled wires, the usage amount of the enameled wires is increased, and a large amount of waste enameled wires are generated.
The waste enameled wire is composed of disassembled electric appliance copper coils and paint-plating defective goods, so that the waste enameled wire contains abundant copper resources, but cannot be directly used as a copper raw material due to the existence of an insulating paint layer.
The metal copper is widely applied to industries such as electric power, machinery, electronics, electrical appliances, weapons, new energy and the like, while the copper ore resources in China are relatively deficient, and the external dependence is more than 70%, which seriously limits the development of the copper industrial chain in China. The recycling of the waste copper resources becomes an important means for making up the shortage of the copper resources in China, and the recycling of the copper in the waste enameled wires has important practical significance.
At present, the method for recovering copper from waste enameled wires is mainly a pyrolysis paint removal method, CN 204080053U discloses a pyrolysis liquating furnace and a production line of waste enameled wires, the pyrolysis liquating furnace and the production line convey crushed waste enameled wires into a furnace pipe of the pyrolysis liquating furnace, the waste enameled wires are pyrolyzed by a natural gas burner and an oil gas burner, a smoke exhaust pipe is arranged at the lower part of the furnace pipe, the smoke exhaust pipe purifies smoke, a blanking hopper at the lower end of the furnace pipe is connected with a crushing winnowing system through a spiral conveyor to produce high-purity copper, and activated carbon is collected and recovered through a dust collection bag. CN 208260486U discloses a tail gas processing apparatus of useless enameled wire pyrolysis liquation stove, and the device carries the exhaust tail gas in the pyrolysis liquation stove to tail gas processing apparatus, handles tail gas effectively.
CN 108735399A discloses a continuous treatment device for waste circuit boards/waste enameled wires based on a pyrolysis liquation principle, which comprises a hearth with a heating cavity inside and a furnace pipe, wherein the furnace pipe is arranged in the heating cavity of the hearth, and the heating cavity is provided with a heating ring cavity surrounding the periphery of the furnace pipe; the furnace pipe is internally provided with a treatment cavity for performing pyrolysis liquation on the waste circuit board/waste enameled wire, and the treatment cavity sequentially forms a preheating region, a pyrolysis region, a gasification region and an aggregate region along the direction from top to bottom of the treatment cavity; the preheating zone is used for dehydration and preheating treatment, the pyrolysis zone cracks organic matters in the waste circuit boards/waste enameled wires, the gasification zone gasifies coke formed by decomposition and separates alloy, and the collection zone gathers metal separated from the alloy, so that the metal in the waste circuit boards/waste enameled wires is recycled.
A paper entitled "thermally treated waste copper enameled wire for copper recovery" was published by zhangmingke et al, which uses a thermal process to remove the insulating varnish of copper enameled wires, and the overall recovery rate can reach 95% (see document "thermally treated waste copper enameled wire for copper recovery", research on renewable resources, 1994, fifth phase, pages 13-19).
However, the insulation paint films of the waste enameled wires are separated by adopting pyrolysis liquation, the equipment cost required by the pyrolysis liquation is high, and the generated tail gas contains a large amount of toxic and harmful gases and is difficult to treat.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for wet separation and copper recovery of a waste enameled wire.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps:
(1) preparing the waste enameled wire into copper rice through pretreatment;
(2) mixing the copper rice and a reducing solution to form a mixture, and then grinding the mixture by a wet method to obtain grinding slurry;
(3) performing cyclone separation on the ground slurry obtained in the step (2) to obtain a bottom flow and overflow mixture;
(4) and (4) performing solid-liquid separation on the obtained underflow in the step (3) to obtain purified copper rice and underflow filtrate, and performing solid-liquid separation on the overflow mixture in the step (3) to obtain waste paint and overflow filtrate.
According to the invention, the insulating paint and the copper in the waste enameled wire are primarily separated by a wet grinding method, and then the copper and the insulating paint are separated by a cyclone separation method according to the density difference of the copper and the insulating paint, so that the waste paint and copper products are obtained.
In addition, during the wet grinding, the copper rice is mixed with the reducing solution, so that the copper is prevented from contacting with oxygen in the air at high temperature generated by grinding, the copper is prevented from being oxidized into copper oxide, and the purity of the purified copper rice and the recovery rate of the copper in the waste enameled wire are ensured; and the underflow filtrate and the overflow filtrate obtained by physical separation can be recycled, so that secondary pollution is avoided, and good social benefit and economic benefit are achieved.
Preferably, the pretreatment in step (1) comprises the following steps: and sequentially carrying out cutting treatment and crushing treatment on the waste enameled wire to prepare the copper rice.
Preferably, the cutting is performed in a cutter and the crushing is performed in a crusher.
According to the invention, the waste enameled wire is cut and crushed into the copper rice through pretreatment, so that the specific surface area of the raw material to be treated is increased, the subsequent grinding effect is favorably improved, the copper rice has certain hardness, the grinding effect is improved by exerting the effect of grinding beads during grinding, and the copper is better separated from the insulating paint.
Preferably, the average length of the copper rice in the step (1) is 5-20mm, for example, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 16mm, 17mm, 18mm, 19mm or 20mm, preferably 5-10 mm.
The waste enameled wire is cut and crushed into the copper rice with the average length of 5-20mm through pretreatment, wherein the shorter the average length of the copper rice is, the more beneficial the subsequent grinding is, and the average length of the copper rice is controlled to be 5-20mm in consideration of the pretreatment time and the pretreatment cost.
Preferably, the concentration of the reducing solution of step (2) is 5 to 15 wt%, for example, may be 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% or 15 wt%, preferably 8 to 12 wt%.
Copper is easily oxidized in air, and if the copper is contacted with oxygen in the air during grinding, the copper is easily oxidized into copper oxide, so that the final recovery rate of the copper is influenced.
Preferably, the reducing component in the reducing solution of step (2) comprises thiosulfate and/or sulfite, preferably a combination of thiosulfate and sulfite. Sulfite has a certain reducing power, and thiosulfate is added to stabilize the reducing power of the reducing solution. The concentration of the reducing solution of the present invention is 5 to 15 wt%, and the mass ratio of thiosulfate to sulfite is (1-5): 1-5, and may be, for example, 1:1, 1:2, 1:3, 1:4, 1:5, 2:1, 2:3, 2:5, 3:1, 3:2, 3:4, 3:5, 4:1, 4:3, 4:5, 5:1, 5:2, 5:3, or 5: 4.
Preferably, the wet grinding of step (2) is performed in a grinder.
Preferably, the liquid level of the reducing solution is higher than the copper meter during the wet grinding in the step (2). The liquid surface of the reducing solution is over the copper rice, so that the copper rice is not contacted with oxygen during grinding, and the copper is prevented from being oxidized.
Preferably, the wet grinding temperature in step (2) is 15-30 deg.C, such as 15 deg.C, 16 deg.C, 17 deg.C, 18 deg.C, 19 deg.C, 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C or 30 deg.C, preferably 20-27 deg.C.
Preferably, the wet grinding time in step (2) is 0.5-8h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h, preferably 2-6 h.
Preferably, the material of the grinding beads used in the wet grinding in step (2) includes any one or a combination of at least two of zirconia, alumina, silicon carbide or copper nanoparticles, and typical but non-limiting combinations include zirconia and copper nanoparticles, alumina and copper nanoparticles, silicon carbide and copper nanoparticles, zirconia, alumina and copper nanoparticles, zirconia, silicon carbide and copper nanoparticles, or zirconia, alumina, silicon carbide and copper nanoparticles. The copper rice can be obtained after the waste enameled wire is pretreated, preferably the copper rice with the average length of 5-10mm, and the copper rice has certain hardness, so that the aim of grinding can be achieved through the interaction between the copper rice in a grinding machine.
Preferably, the cyclonic separation of step (3) is carried out in a cyclone.
Preferably, the feed pressure of the grinding slurry in the cyclone separation in step (3) is 0.3 to 0.6MPa, and may be, for example, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa or 0.6MPa, preferably 0.4 to 0.5 MPa.
The method adopts cyclone separation to separate the copper and the waste paint in the grinding slurry, the density of the copper and the waste paint is different, and the waste paint with lower density is separated from the copper with higher density through the cyclone separation.
Preferably, the solid-liquid separation underflow method in step (4) comprises a screening separation method and/or a settling separation method.
Preferably, the method for filtering the overflow mixture in the step (4) comprises a plate-and-frame filter pressing method and/or a centrifugal separation method.
The screening separation method, the settling separation method, the plate-and-frame filter pressing method and the centrifugal separation method are conventional technical means in the field, and a person skilled in the art can select parameters in the screening separation method, the settling separation method, the plate-and-frame filter pressing method and the centrifugal separation method according to actual needs, and the invention is not described herein again.
Preferably, the underflow filtrate and the overflow filtrate in the step (4) are mixed and then returned to the step (2) as the reducing solution. The reducing components in the underflow filtrate and the overflow filtrate are sodium thiosulfate and/or sodium sulfite, and the underflow filtrate and the overflow filtrate can be used as a reducing solution to return to the step (2) for grinding the copper rice after being mixed.
Preferably, the method further comprises a post-treatment step (5) after step (4): and (5) drying the purified copper rice in the step (4), and preparing a copper product from the dried purified copper rice.
Preferably, the copper product comprises any one of or a combination of at least two of a copper plate, a copper wire, a copper sheet or a copper ingot.
As a preferred technical scheme of the method, the method comprises the following steps:
(1) sequentially carrying out cutting treatment and crushing treatment on the waste enameled wire to prepare copper rice with the average length of 5-20 mm;
(2) mixing the copper rice and 5-15 wt% thiosulfate and/or sulfite solution to form a mixture, and then wet-grinding the mixture in a grinding machine to obtain grinding slurry, wherein the wet-grinding temperature is 15-30 ℃, the wet-grinding time is 0.5-8h, the liquid level of the thiosulfate and/or sulfite solution does not exceed the copper rice during wet-grinding, and the grinding beads used during wet-grinding comprise any one or the combination of at least two of zirconia, alumina, silicon carbide and copper rice;
(3) separating the grinding slurry obtained in the step (2) in a cyclone by using a cyclone, wherein the feeding pressure of the grinding slurry is 0.3-0.6MPa, and obtaining a mixed material of underflow and overflow;
(4) obtaining the bottom flow obtained in the solid-liquid separation step (3) to obtain purified copper rice and bottom flow filtrate, obtaining waste paint and overflow filtrate from the overflow mixture obtained in the solid-liquid separation step (3), and returning the mixture to the step (2) as a reducing solution after the bottom flow filtrate and the overflow filtrate are mixed;
(5) and (4) drying the purified copper rice in the step (4), and preparing the dried purified copper rice into any one or a mixture of at least two of a copper plate, a copper wire, a copper sheet or a copper ingot.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the copper in the waste enameled wire is separated from the insulating paint by a method combining wet grinding and cyclone separation, so that the defects of high energy consumption and toxic and harmful gas generation caused by paint burning in the traditional technology are overcome;
(2) the method for wet separation and copper recovery of the waste enameled wire provided by the invention is simple to operate, low in energy consumption, low in equipment investment and free from secondary pollution, the purity of copper in the recovered copper product can reach 99.0 wt%, the recovery rate of copper in the waste enameled wire can reach 98.8%, and the method has important industrial popularization value.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps:
(1) cutting the waste enameled wire in a cutting machine, and then crushing in a crusher to obtain copper rice with the average length of 10 mm;
(2) mixing the copper rice and a reducing solution with the concentration of 10 wt% to form a mixture, and then grinding the mixture in a grinding machine in a wet method to obtain grinding slurry, wherein the reducing solution is a mixed solution of sodium thiosulfate and sodium sulfite, the mass ratio of the sodium thiosulfate to the sodium sulfite is 1:1, the wet grinding temperature is 25 ℃, the wet grinding time is 3 hours, grinding beads used in the wet grinding are copper rice, and the reducing solution does not cover the copper rice in the wet grinding;
(3) separating the grinding slurry obtained in the step (2) in a cyclone by using a cyclone, wherein the feeding pressure of the grinding slurry is 0.4MPa, so as to obtain a mixed material of underflow and overflow;
(4) screening and separating the underflow obtained in the step (3) to obtain purified copper rice and underflow filtrate, press-filtering the overflow mixture obtained in the step (3) by using a plate frame to obtain waste paint and overflow filtrate, and returning the mixed underflow filtrate and overflow filtrate to the step (2) as a reduction solution;
(5) and (5) drying the purified copper rice obtained in the step (4), and stamping and pressing the dried purified copper rice by using a copper plate die to obtain a copper plate product, wherein the purity of copper in the obtained copper plate product reaches 96.3 wt%.
In this example, the copper in the waste enameled wire was recovered, and the recovery rate of copper was 98.6%.
Example 2
The embodiment provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps:
(1) cutting the waste enameled wire in a cutting machine, and then crushing in a crusher to obtain copper rice with the average length of 8 mm;
(2) mixing the copper rice and a reducing solution with the concentration of 12 wt% to form a mixture, and then wet-grinding the mixture in a grinder to obtain grinding slurry, wherein the reducing solution is a mixed solution of sodium thiosulfate and sodium sulfite, the mass ratio of the sodium thiosulfate to the sodium sulfite is 3:1, the wet-grinding temperature is 20 ℃, the wet-grinding time is 6 hours, grinding beads with the diameter of 8mm are made of silicon carbide during wet-grinding, and the reducing solution does not cover the copper rice during wet-grinding;
(3) separating the grinding slurry obtained in the step (2) in a cyclone by using a cyclone, wherein the feeding pressure of the grinding slurry is 0.45MPa, so as to obtain a mixed material of underflow and overflow;
(4) settling and separating the bottom flow obtained in the step (3) to obtain purified copper rice and bottom flow filtrate, performing plate and frame filter pressing on the overflow mixture obtained in the step (3) to obtain waste paint and overflow filtrate, and returning the mixture of the bottom flow filtrate and the overflow filtrate as a reduction solution to the step (2);
(5) and (5) drying the purified copper rice obtained in the step (4), and stamping and pressing the dried purified copper rice by using a copper ingot mould to obtain a copper ingot product, wherein the purity of copper in the obtained copper ingot product reaches 99.0 wt%.
In the embodiment, the copper in the waste enameled wire is recovered, and the recovery rate of the copper is 98.8%.
Example 3
The embodiment provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps:
(1) cutting the waste enameled wire in a cutting machine, and then crushing in a crusher to obtain copper rice with the average length of 5 mm;
(2) mixing the copper rice and a reducing solution with the concentration of 8 wt% to form a mixture, and then wet-grinding the mixture in a grinder to obtain grinding slurry, wherein the reducing solution is a mixed solution of sodium thiosulfate and sodium sulfite, the mass ratio of the sodium thiosulfate to the sodium sulfite is 1:3, the wet-grinding temperature is 27 ℃, the wet-grinding time is 2 hours, grinding beads with the diameter of 5mm are made of aluminum oxide during wet-grinding, and the reducing solution does not cover the copper rice during wet-grinding;
(3) separating the grinding slurry obtained in the step (2) in a cyclone by using a cyclone, wherein the feeding pressure of the grinding slurry is 0.5MPa, and obtaining a mixed material of underflow and overflow;
(4) settling and separating the underflow obtained in the step (3) to obtain purified copper rice and underflow filtrate, centrifuging the overflow mixture obtained in the step (3) to obtain waste paint and overflow filtrate, and mixing the underflow filtrate and the overflow filtrate to be used as a reducing solution to return to the step (2);
(5) and (5) air-drying the purified copper rice obtained in the step (4), and rolling and pressing the dried purified copper rice by using a copper plate die to obtain a copper sheet product, wherein the purity of copper in the obtained copper sheet product reaches 95.4 wt%.
In this example, the copper in the waste enameled wire was recovered, and the recovery rate of copper was 98.5%.
Example 4
The embodiment provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps:
(1) cutting the waste enameled wire in a cutting machine, and then crushing in a crusher to obtain copper rice with the average length of 15 mm;
(2) mixing the copper rice and a reducing solution with the concentration of 15 wt% to form a mixture, and then wet-grinding the mixture in a grinder to obtain grinding slurry, wherein the reducing solution is a mixed solution of sodium thiosulfate and sodium sulfite, the mass ratio of potassium thiosulfate to potassium sulfite is 1:5, the wet-grinding temperature is 15 ℃, the wet-grinding time is 8 hours, grinding beads with the diameter of 8mm are made of zirconium oxide during wet-grinding, and the reducing solution does not cover the copper rice during wet-grinding;
(3) separating the grinding slurry obtained in the step (2) in a cyclone by using a cyclone, wherein the feeding pressure of the grinding slurry is 0.6MPa, so as to obtain a mixed material of underflow and overflow;
(4) settling and separating the underflow obtained in the step (3) to obtain purified copper rice and underflow filtrate, centrifuging the overflow mixture obtained in the step (3) to obtain waste paint and overflow filtrate, and mixing the underflow filtrate and the overflow filtrate to be used as a reducing solution to return to the step (2);
(5) and (5) drying the purified copper rice obtained in the step (4), and stamping and pressing the dried purified copper rice by using a copper plate die to obtain a copper plate product, wherein the purity of copper in the obtained copper plate product reaches 94.6 wt%.
In this example, the copper in the waste enameled wire was recovered, and the recovery rate of copper was 98.1%.
Example 5
The embodiment provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps:
(1) cutting the waste enameled wire in a cutting machine, and then crushing in a crusher to obtain copper rice with the average length of 20 mm;
(2) mixing the copper rice and a reducing solution with the concentration of 5 wt% to form a mixture, and then wet-grinding the mixture in a grinder to obtain grinding slurry, wherein the reducing solution is a mixed solution of sodium thiosulfate and sodium sulfite, the mass ratio of the sodium thiosulfate to the sodium sulfite is 5:1, the wet-grinding temperature is 30 ℃, the wet-grinding time is 0.5h, grinding beads with the diameter of 8mm used in the wet-grinding are made of zirconium oxide, and the reducing solution does not cover the copper rice in the wet-grinding;
(3) separating the grinding slurry obtained in the step (2) in a cyclone by using a cyclone, wherein the feeding pressure of the grinding slurry is 0.3MPa, and obtaining a mixed material of underflow and overflow;
(4) settling and separating the underflow obtained in the step (3) to obtain purified copper rice and underflow filtrate, centrifuging the overflow mixture obtained in the step (3) to obtain waste paint and overflow filtrate, and mixing the underflow filtrate and the overflow filtrate to be used as a reducing solution to return to the step (2);
(5) and (5) drying the purified copper rice obtained in the step (4), and rolling and pressing the dried purified copper rice by using a copper plate die to obtain a copper sheet product, wherein the purity of copper in the obtained copper sheet product reaches 92.1 wt%.
In the embodiment, the copper in the waste enameled wire is recovered, and the recovery rate of the copper is 98.2%.
Example 6
This example provides a wet separation and copper recovery method for waste enameled wire, which is the same as example 2 except that the reducing solution used is a 12 wt% ethylene glycol solution.
The glycol solution has certain viscosity, and the purified copper particles and the glycol solution can not be separated completely, so the purity of the obtained copper product is reduced, the copper purity of the obtained copper ingot product is 86.1 wt% through determination, and the glycol is easy to be attached to a plate frame during plate frame filter pressing, which is not beneficial to long-term stable solid-liquid separation.
In this example, the copper in the waste enameled wire was recovered, and the recovery rate of copper was 98.5%.
Comparative example 1
The comparative example provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps:
(1) cutting the waste enameled wire in a cutting machine, and then crushing in a crusher to obtain copper rice with the average length of 8 mm;
(2) mixing the copper rice and absolute ethyl alcohol to form a mixture, and then wet-grinding the mixture in a grinding machine to obtain grinding slurry, wherein the wet-grinding temperature is 20 ℃, the wet-grinding time is 6 hours, grinding beads with the diameter of 8mm are made of silicon carbide during wet-grinding, and the absolute ethyl alcohol does not cover the copper rice during wet-grinding;
(3) separating the grinding slurry obtained in the step (2) in a cyclone by using a cyclone, wherein the feeding pressure of the grinding slurry is 0.45MPa, so as to obtain a mixed material of underflow and overflow;
(4) settling and separating the bottom flow obtained in the step (3) to obtain purified copper rice and bottom flow filtrate, press-filtering the overflow mixture obtained in the step (3) by using a plate frame to obtain waste paint and overflow filtrate, and returning the mixture of the bottom flow filtrate and the overflow filtrate to the step (2) as absolute ethyl alcohol after mixing;
(5) and (5) drying the purified copper rice obtained in the step (4), and stamping and pressing the dried purified copper rice by using a copper ingot mould to obtain a copper ingot product, wherein the purity of copper in the obtained copper ingot product reaches 98.8 wt%.
Comparative example 1 wet separation treatment was performed on the waste enameled wire, the purity of the recovered copper was 98.8 wt%, but absolute ethyl alcohol was easily volatilized, and absolute ethyl alcohol was required to be continuously supplemented in the wet grinding process, so the cost of wet grinding in comparative example 1 was high. And the absolute ethyl alcohol has no reducibility, although the purity of copper in the copper product can reach 98.8 wt%, part of copper is oxidized into copper oxide, so that the loss of copper in wet grinding is caused, and the recovery rate of copper is reduced to 97.3%.
Comparative example 2
The comparative example provides a method for wet separation and copper recovery of a waste enameled wire, which is the same as the comparative example 1 except that the absolute ethyl alcohol used in the step (2) is replaced by water.
The water has no reducibility, although the purity of copper in the copper product can reach 99 wt%, part of copper is oxidized into copper oxide, which causes the loss of copper during wet grinding, and the recovery rate of copper is reduced to 97.5%.
Comparative example 3
The comparative example provides a method for wet separation and copper recovery of waste enameled wires, which comprises the following steps:
(1) cutting the waste enameled wire in a cutting machine, and then crushing in a crusher to obtain copper rice with the average length of 8 mm;
(2) mixing the copper rice and a reducing solution with the concentration of 12 wt% to form a mixture, and then wet-grinding the mixture in a grinder to obtain grinding slurry, wherein the reducing solution is a mixed solution of sodium thiosulfate and sodium sulfite, the mass ratio of the sodium thiosulfate to the sodium sulfite is 3:1, the wet-grinding temperature is 20 ℃, the wet-grinding time is 6 hours, grinding beads with the diameter of 8mm are made of silicon carbide during wet-grinding, and the reducing solution does not cover the copper rice during wet-grinding;
(3) and (3) screening and separating the grinding slurry obtained in the step (2) to obtain purified copper rice and filtrate, and returning the filtrate to the step (2) as a reducing solution.
The copper and the waste paint can not be effectively separated by adopting the screening separation method to treat the grinding slurry, and a large amount of waste paint is remained on the surface of the copper after the filtration is finished, so that the obtained purified copper rice can not be directly applied to the preparation of copper products.
In conclusion, the method combines the wet grinding and the cyclone separation, so that the copper in the waste enameled wire is separated from the insulating paint, and the reducing solution is added in the wet grinding process, so that the recovery rate of the copper in the waste enameled wire is ensured. The method provided by the invention is simple to operate, low in energy consumption, low in equipment investment and free of secondary pollution, the purity of copper in the recovered copper product can reach 99%, and the recovery rate of copper in the waste enameled wire can reach 98.8%.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (22)
1. A method for wet separation and copper recovery of waste enameled wires is characterized by comprising the following steps:
(1) preparing the waste enameled wires into copper rice through pretreatment;
(2) mixing the copper rice and a reducing solution to form a mixture, and then grinding the mixture by a wet method to obtain grinding slurry;
(3) performing cyclone separation on the ground slurry obtained in the step (2) to obtain a bottom flow and overflow mixture;
(4) separating the underflow obtained in the step (3) by solid-liquid separation to obtain purified copper rice and underflow filtrate, and separating the overflow mixture obtained in the step (3) by solid-liquid separation to obtain waste paint and overflow filtrate;
the reducing components in the reducing solution in the step (2) comprise thiosulfate and sulfite;
the mass ratio of the thiosulfate to the sulfinate is (1-5): (1-5);
and (4) mixing the underflow filtrate and the overflow filtrate, and returning the mixture to the step (2) as a reducing solution.
2. The method according to claim 1, wherein the pretreatment of step (1) comprises the steps of: and sequentially carrying out cutting treatment and crushing treatment on the waste enameled wire to prepare the copper rice.
3. Method according to claim 2, characterized in that the cutting is carried out in a cutter and the crushing is carried out in a crusher.
4. The method of claim 2, wherein the average length of the copper meters of step (1) is 5-20 mm.
5. The method of claim 4, wherein the average length of the copper meters of step (1) is 5-10 mm.
6. The method according to claim 1, wherein the concentration of the reducing solution of step (2) is 5 to 15 wt%.
7. The method according to claim 6, wherein the concentration of the reducing solution of the step (2) is 8 to 12 wt%.
8. The method of claim 1, wherein the wet grinding of step (2) is performed in a grinding mill.
9. The method of claim 1, wherein the wet grinding of step (2) is performed such that the surface of the reducing solution is above the copper meter.
10. The method of claim 1, wherein the temperature of the wet grinding in step (2) is 15-30 ℃.
11. The method of claim 10, wherein the temperature of the wet grinding in step (2) is 20-27 ℃.
12. The method of claim 1, wherein the wet grinding time in step (2) is 0.5-8 h.
13. The method of claim 12, wherein the wet grinding time of step (2) is 2-6 h.
14. The method according to claim 1, wherein the material of the grinding beads used in the wet grinding in step (2) comprises any one or a combination of at least two of zirconia, alumina, silicon carbide or copper nanoparticles.
15. The method of claim 1, wherein the cyclonic separation of step (3) is performed in a cyclone.
16. The method according to claim 1, wherein the feeding pressure of the grinding slurry in the cyclone separation in the step (3) is 0.3-0.6 MPa.
17. The method according to claim 16, wherein the feeding pressure of the grinding slurry in the cyclone separation in the step (3) is 0.4-0.5 MPa.
18. The process of claim 1, wherein the solid-liquid separation underflow of step (4) comprises a sieve separation process and/or a settling separation process.
19. The method of claim 1, wherein the solid-liquid separation of the overflow mix of step (4) comprises a plate-and-frame filter press process and/or a centrifugal separation process.
20. The method according to claim 1, characterized in that it further comprises a post-treatment step (5) after step (4): and (5) drying the purified copper rice in the step (4), and preparing a copper product from the dried purified copper rice.
21. The method of claim 20, wherein the copper product comprises any one of or a combination of at least two of a copper plate, a copper wire, a copper sheet, or a copper ingot.
22. Method according to claim 1, characterized in that it comprises the following steps:
(1) sequentially carrying out cutting treatment and crushing treatment on the waste enameled wire to prepare copper rice with the average length of 5-20 mm;
(2) mixing the copper rice, 5-15 wt% thiosulfate and sulfite solution to form a mixture, and then wet-grinding the mixture in a grinder to obtain grinding slurry, wherein the wet-grinding temperature is 15-30 ℃, the wet-grinding time is 0.5-8h, the liquid level of the thiosulfate and sulfite solution is beyond the copper rice during wet-grinding, and the grinding beads used during wet-grinding comprise any one or the combination of at least two of zirconia, alumina, silicon carbide and copper rice;
(3) separating the grinding slurry obtained in the step (2) in a cyclone by using a cyclone, wherein the feeding pressure of the grinding slurry is 0.3-0.6MPa, and obtaining a mixed material of underflow and overflow;
(4) obtaining the bottom flow obtained in the solid-liquid separation step (3) to obtain purified copper rice and bottom flow filtrate, obtaining waste paint and overflow filtrate from the overflow mixture obtained in the solid-liquid separation step (3), and returning the mixture to the step (2) as a reducing solution after the bottom flow filtrate and the overflow filtrate are mixed;
(5) and (4) drying the purified copper rice in the step (4), and making the dried purified copper rice into any one or a combination of at least two of a copper plate, a copper wire, a copper sheet or a copper ingot.
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| US8834715B2 (en) * | 2011-03-15 | 2014-09-16 | Kabushiki Kaisha Toshiba | Copper recovery apparatus and copper recovery method |
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Address after: 244000 Tongling Qisheng metal recycling resources Co., Ltd., Jinqiao Industrial Park, Yi'an District, Tongling City, Anhui Province Patentee after: Tongling Fuxiang copper based material technology Co.,Ltd. Patentee after: Institute of Process Engineering, Chinese Academy of Sciences Address before: 244000 Tongling Qisheng metal recycling resources Co., Ltd., Jinqiao Industrial Park, Yi'an District, Tongling City, Anhui Province Patentee before: TONGLING FUXIANG COPPER RECYCLING Co.,Ltd. Patentee before: Institute of Process Engineering, Chinese Academy of Sciences |