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.
CN 108735399A discloses continuous processing equipment to useless circuit board/useless enameled wire based on pyrolysis liquifaction principle, continuous processing equipment includes that inside has furnace and the stove courage in heating chamber of heating chamber, and the stove courage is arranged in the heating intracavity of furnace, and has the heating ring chamber around the stove courage periphery in the heating chamber. 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 subjected to dehydration and preheating treatment, organic matters in the waste circuit boards/waste enameled wires are cracked by the pyrolysis zone, coke formed by decomposition is gasified and alloy is separated by the gasification zone, and metal separated from the alloy is gathered by the collection zone; the recycling of metal in the waste circuit board/waste enameled wire is realized, but the coke is directly gasified in the gasification area, and partial copper particles are taken away by the gasification of the coke, so that the loss of copper resources is caused.
CN 104096842A discloses a production process of high-purity copper powder by using waste enameled wires, which sequentially performs sorting, cleaning and spin-drying operations on the waste enameled wires, wherein the sorting operation conditions capillary copper paint with the diameter of 0.04-0.1 mm; sending the picked capillary copper enameled wires into a liquating furnace in a sealed and oxygen-free environment for heating and pyrolysis, and performing forced cooling after pyrolysis; carrying out crushing and winnowing treatment on the furnace burden formed by heating and pyrolyzing the liquating furnace and then cooling to ensure that the furnace burden is coarsely crushed and activated carbon ash generated by pyrolysis is removed; and performing ball milling or turbine self-cooling crushing and screening operation on the furnace burden in sequence to obtain the high-purity copper powder. The method uses crushing and winnowing treatment to treat the activated carbon ash generated by pyrolysis, but the activated carbon ash is mixed with part of copper particles, so that the loss of copper resources is caused.
CN 108039253 a discloses a waste enameled wire paint removing system and an ash pushing mechanism, which are used for adjusting a temperature adjusting mechanism in a smoke exhaust pipeline, the ash pushing system recovers adverse effects caused by deposition adsorption of substances such as dust, carbon black and gas tar in pyrolysis smoke and in the pipeline, the reliability of the enameled wire paint removing system is significantly improved, but the mechanism only pushes away the ash pushing system, and the carbon black generated by pyrolysis 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, no study was made on how to separate copper from char in the ash produced by pyrolysis.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing carbon black and co-producing copper chloride by using waste enameled wires, which not only can recover copper in the waste enameled wires, but also can deeply separate a copper-carbon mixture generated by pyrolyzing the waste enameled wires to prepare carbon black and copper chloride.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing carbon black and co-producing copper chloride by using waste enameled wires, which comprises the following steps:
(1) pyrolyzing the waste enameled wires to obtain a pyrolysis material;
(2) cooling the pyrolysis material obtained in the step (1), and then screening to obtain a mixture of a copper simple substance and copper carbon;
(3) mixing hydrochloric acid with the copper-carbon mixture obtained in the step (2), then carrying out dissolution reaction, and carrying out solid-liquid separation to obtain a copper chloride solution and solid particles;
(4) and (4) washing the solid particles obtained in the step (3), and drying to obtain the carbon black.
According to the invention, a pyrolysis material obtained after pyrolysis of the waste enameled wire is separated, and then the obtained copper-carbon mixture is reacted with hydrochloric acid to obtain a copper chloride solution and solid particles, and the solid particles are washed and dried to obtain the carbon black.
According to the invention, the copper chloride solution and the carbon black are obtained by reacting the copper-carbon mixture with hydrochloric acid, the copper-carbon mixture is recycled, the utilization rate of resources in the waste enameled wire is improved, and the stacking hazard of ash slag generated by pyrolysis of the waste enameled wire is reduced.
Preferably, the temperature of the pyrolysis treatment in the step (1) is 700-900 ℃, for example 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, preferably 750-850 ℃.
Preferably, the pyrolysis treatment in step (1) is carried out for 0.5 to 2 hours, such as 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour, 1.1 hour, 1.2 hour, 1.3 hour, 1.4 hour, 1.5 hour, 1.6 hour, 1.7 hour, 1.8 hour, 1.9 hour or 2 hours, preferably 1 to 1.5 hours.
Preferably, the cooling method in the step (2) comprises spray water cooling.
According to the invention, after pyrolysis of the waste enameled wire, the insulating paint is pyrolyzed to obtain carbon black doped with copper particles, and the obtained carbon black is separated from the surface of a copper simple substance in the waste enameled wire.
Preferably, the cooling in step (2) is completed within 1-20min after the pyrolysis is finished, and may be 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min, for example.
The cooling is finished within 1-20min after the pyrolysis is finished, namely, the temperature of the pyrolysis material is reduced to room temperature within 1-20min after the pyrolysis is finished by a spray water cooling method, wherein the room temperature comprises 15-30 ℃, and can be 15 ℃, 18 ℃, 20 ℃, 24 ℃, 25 ℃, 27 ℃ or 30 ℃.
The temperature of the carbon black doped with copper particles after pyrolysis is high, and at the moment, the mixture of copper simple substance and copper carbon is easy to separate. If the cooling operation is not performed immediately after the pyrolysis is finished, the temperature of the copper-carbon mixture is naturally reduced, and the copper-carbon mixture is not easily separated from the copper simple substance.
Preferably, the acid of step (3) comprises any one of hydrochloric acid, nitric acid or sulfuric acid or a combination of at least two thereof, typical but non-limiting combinations include a combination of hydrochloric acid and nitric acid, a combination of hydrochloric acid and sulfuric acid, a combination of nitric acid and sulfuric acid or a combination of hydrochloric acid, nitric acid and sulfuric acid.
Preferably, the concentration of the acid in the step (3) is 100-200g/L, such as 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L or 200g/L, preferably 120-180 g/L.
Preferably, the temperature of the dissolution reaction in step (3) is 30-50 ℃, for example, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃ or 50 ℃, preferably 35-45 ℃.
Preferably, the dissolution reaction time in step (3) is 0.5 to 2 hours, and may be, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, preferably 1 to 1.5 h.
Preferably, the liquid-solid ratio of the hydrochloric acid and the copper-carbon mixture in the step (3) is 3-6mL/g, for example, 3mL/g, 3.5mL/g, 4mL/g, 4.5mL/g, 5mL/g, 5.5mL/g or 6mL/g, preferably 4-5 mL/g.
Preferably, the method further comprises the step of ball milling the copper-carbon mixture to a particle size of 325 mesh or less before mixing the hydrochloric acid with the copper-carbon mixture
Copper and compounds thereof in the copper-carbon mixture obtained by the method are wrapped by carbon, and in order to realize good separation of the copper, copper oxide and carbon black, the copper-carbon mixture is ball-milled by a ball milling method until the granularity is less than or equal to 325 meshes, so that the separation of the carbon black, the copper and the copper oxide is realized, the specific surface area of the copper, the copper oxide and the carbon black is increased, the copper oxide and the carbon black are easier to perform a dissolution reaction, and the efficiency of the dissolution reaction is improved.
The invention improves the specific surface area of copper and carbon black in the copper-carbon mixture by ball milling, so that the copper is easier to perform a dissolution reaction with acid, and the efficiency of the dissolution reaction is improved.
Preferably, the ball milling time is 2 to 5h, for example 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, preferably 3 to 4 h.
Preferably, the washing in step (4) is washing with water.
Preferably, the liquid-solid ratio of the washing water to the solid particles is (1-3: 1), and may be, for example, 1:1, 1.5:1, 2:1, 2.5:1 or 3: 1.
Preferably, the solution generated after the washing in the step (4) is returned to the step (3) and mixed with acid for dissolution reaction.
Preferably, the drying method in step (4) is a conventional drying method, including but not limited to vacuum drying, air drying or oven drying, and can be reasonably selected by one skilled in the art according to actual needs.
As a preferred technical scheme of the method, the method comprises the following steps:
(1) pyrolyzing the waste enameled wire at the temperature of 700 ℃ and 900 ℃ for 0.5-2h to obtain a pyrolysis material;
(2) spraying water to the pyrolysis material obtained in the step (1) within 1-20min after pyrolysis is finished, then screening to obtain a mixture of a copper simple substance and copper carbon, and ball-milling the mixture of the copper carbon until the granularity is less than or equal to 325 meshes;
(3) mixing hydrochloric acid with the concentration of 100-200g/L and the copper-carbon mixture obtained in the step (2) according to the liquid-solid ratio of 3-6mL/g, then carrying out a dissolution reaction at the temperature of 30-50 ℃ for 0.5-2h, and carrying out solid-liquid separation to obtain a copper chloride solution and solid particles;
(4) and (4) washing the solid particles obtained in the step (3) according to the liquid-solid ratio (1-3) to 1, and drying to obtain the carbon black.
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:
the method comprises the steps of firstly converting an insulating layer outside the waste enameled wire into a copper-carbon mixture through pyrolysis, wherein the copper-carbon mixture contains copper and oxides thereof, and converting the copper and the oxides thereof in the copper-carbon mixture into copper chloride through a dissolving reaction of the copper-carbon mixture and hydrochloric acid, so that carbon black and copper are separated.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
The copper ion concentration and the chloride ion concentration in the examples and comparative examples of the present invention were measured by ion chromatography.
Example 1
The embodiment provides a method for preparing carbon black and co-producing copper chloride by using waste enameled wires, which comprises the following steps:
(1) pyrolyzing the waste enameled wire for 1h at 800 ℃ in a pyrolysis furnace to obtain a pyrolysis material;
(2) after the pyrolysis material is discharged from the pyrolysis furnace, spraying water to cool to 20 ℃ within 10min, screening to obtain a mixture of a copper simple substance and copper carbon, and ball-milling the mixture of the copper carbon until the granularity is less than or equal to 325 meshes;
(3) mixing hydrochloric acid with the concentration of 150g/L and the copper-carbon mixture obtained in the step (2) after ball milling according to the liquid-solid ratio of 5mL/g, then carrying out dissolution reaction at the temperature of 40 ℃ for 1h, and carrying out solid-liquid separation to obtain a copper chloride solution and solid particles;
(4) and (4) washing the solid particles obtained in the step (3) according to a liquid-solid ratio of 2:1, wherein the copper ion content in the obtained copper chloride solution is 13 wt%, and the chloride ion content in the carbon black is 0.6 wt%.
Example 2
The embodiment provides a method for preparing carbon black and co-producing copper chloride by using waste enameled wires, which comprises the following steps:
(1) pyrolyzing the waste enameled wire for 1.5h at 750 ℃ in a pyrolysis furnace to obtain a pyrolysis material;
(2) after the pyrolysis material is discharged from the pyrolysis furnace, spraying water to cool to 25 ℃ within 15min, screening to obtain a mixture of a copper simple substance and copper carbon, and ball-milling the mixture of the copper carbon until the granularity is less than or equal to 325 meshes;
(3) mixing hydrochloric acid with the concentration of 180g/L and the copper-carbon mixture obtained in the step (2) after ball milling according to the liquid-solid ratio of 4mL/g, then carrying out dissolution reaction at the temperature of 45 ℃ for 1h, and carrying out solid-liquid separation to obtain a copper chloride solution and solid particles;
(4) and (4) washing the solid particles obtained in the step (3) according to the liquid-solid ratio of 2.5:1, wherein the copper ion content in the obtained copper chloride solution is 10.7 wt%, and the chloride ion content in the carbon black is 0.3 wt%.
Example 3
The embodiment provides a method for preparing carbon black and co-producing copper chloride by using waste enameled wires, which comprises the following steps:
(1) pyrolyzing the waste enameled wire for 1h at 850 ℃ in a pyrolysis furnace to obtain a pyrolysis material;
(2) after the pyrolysis material is discharged from the pyrolysis furnace, spraying water to cool to 25 ℃ within 5min, screening to obtain a mixture of a copper simple substance and copper carbon, and ball-milling the mixture of the copper carbon until the granularity is less than or equal to 325 meshes;
(3) mixing hydrochloric acid with the concentration of 120g/L and the copper-carbon mixture obtained in the step (2) after ball milling according to the liquid-solid ratio of 5mL/g, then carrying out dissolution reaction at the temperature of 35 ℃ for 1.5h, and carrying out solid-liquid separation to obtain a copper chloride solution and solid particles;
(4) and (4) washing the solid particles obtained in the step (3) according to the liquid-solid ratio of 1.5:1, wherein the copper ion content in the obtained copper chloride solution is 17 wt%, and the chloride ion content in the carbon black is 0.3 wt%.
Example 4
The embodiment provides a method for preparing carbon black and co-producing copper chloride by using waste enameled wires, which comprises the following steps:
(1) pyrolyzing the waste enameled wires for 2 hours at 700 ℃ in a pyrolysis furnace to obtain a pyrolysis material;
(2) after the pyrolysis material is discharged from the pyrolysis furnace, spraying water to cool to 25 ℃ within 20min, screening to obtain a mixture of a copper simple substance and copper carbon, and ball-milling the mixture of the copper carbon until the granularity is less than or equal to 325 meshes;
(3) mixing hydrochloric acid with the concentration of 100g/L and the copper-carbon mixture obtained in the step (2) after ball milling according to the liquid-solid ratio of 6mL/g, then carrying out dissolution reaction at the temperature of 30 ℃ for 2h, and carrying out solid-liquid separation to obtain a copper chloride solution and solid particles;
(4) and (4) washing the solid particles obtained in the step (3) according to a liquid-solid ratio of 1:1, wherein the copper ion content in the obtained copper chloride solution is 16 wt%, and the chloride ion content in the carbon black is 1 wt%.
Example 5
The embodiment provides a method for preparing carbon black and co-producing copper chloride by using waste enameled wires, which comprises the following steps:
(1) pyrolyzing the waste enameled wires for 0.5h at 900 ℃ in a pyrolysis furnace to obtain a pyrolysis material;
(2) after the pyrolysis material is discharged from the pyrolysis furnace, spraying water to cool to 25 ℃ within 20min, screening to obtain a mixture of a copper simple substance and copper carbon, and ball-milling the mixture of the copper carbon until the granularity is less than or equal to 325 meshes;
(3) mixing hydrochloric acid with the concentration of 200g/L and the copper-carbon mixture obtained in the step (2) after ball milling according to the liquid-solid ratio of 3mL/g, then carrying out dissolution reaction at the temperature of 50 ℃ for 0.5h, and carrying out solid-liquid separation to obtain a copper chloride solution and solid particles;
(4) and (4) washing the solid particles obtained in the step (3) according to a liquid-solid ratio of 3:1, wherein the copper ion content in the obtained copper chloride solution is 9 wt%, and the chloride ion content in the carbon black is 0.3 wt%.
Example 6
This example provides a method for co-production of copper chloride from carbon black using waste enameled wire, which is the same as example 5 except that the hydrochloric acid concentration in step (3) is 240 g/L.
The content of copper ions in the finally obtained copper chloride solution is 7 wt%, the content of chloride ions in the carbon black is 0.5 wt%, and when the concentration of hydrochloric acid is 240g/L, copper in the copper-carbon mixture reacts with the hydrochloric acid to generate cuprous chloride, the cuprous chloride is difficult to dissolve, the further dissolution reaction of copper is influenced, the conversion rate of copper is reduced, and the purity of the obtained carbon black is reduced.
Example 7
This example provides a method for co-production of copper chloride from carbon black using waste enameled wire, which is the same as example 3 except that the hydrochloric acid concentration in step (3) is 80 g/L.
The content of copper ions in the finally obtained copper chloride solution is 8 wt%, the content of chloride ions in the carbon black is 0.8%, but when the concentration of hydrochloric acid is 80g/L, copper in the copper-carbon mixture cannot be completely converted into copper chloride, and the purity of the obtained carbon black is reduced.
Comparative example 1
This comparative example provides a method for recycling a waste enameled wire, which is the same as example 1 except that the acid used in step (3) is sulfuric acid having a concentration of 150 g/L.
The reaction of concentrated sulfuric acid with copper produces insoluble CuS, which is difficult to dissolve and affects the further dissolution reaction of copper, making the dissolution reaction unable to proceed smoothly.
Comparative example 2
This comparative example provides a method for recycling a waste enameled wire, which is the same as example 1 except that the acid used in step (3) is nitric acid having a concentration of 150 g/L.
The copper ion content of the obtained copper nitrate solution is 11 wt%, and the nitrate ion content of the carbon black is 10 wt%.
The nitric acid and the copper-carbon mixture generate a large amount of nitric oxide toxic gas during reaction, which is not beneficial to environmental protection.
In conclusion, the insulating layer outside the waste enameled wire is converted into the carbon black through pyrolysis, the carbon black contains copper impurities, the copper in the copper-carbon mixture is converted into the copper chloride through the dissolution reaction of the copper-carbon mixture and the acid, the carbon black is separated from the copper, the content of the impurity ions in the obtained carbon black is as low as 0.3 wt%, and the method is simple to operate and has important industrial popularization value.
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.