CN113096884A - Preparation method of high-purity copper bar - Google Patents

Preparation method of high-purity copper bar Download PDF

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Publication number
CN113096884A
CN113096884A CN202110353852.9A CN202110353852A CN113096884A CN 113096884 A CN113096884 A CN 113096884A CN 202110353852 A CN202110353852 A CN 202110353852A CN 113096884 A CN113096884 A CN 113096884A
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copper
copper bar
cooling
purity
temperature
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周涛
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Jiangxi Zhongsheng Metal Co ltd
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Jiangxi Zhongsheng Metal Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • H01R43/16Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for manufacturing contact members, e.g. by punching and by bending

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  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a preparation method of a high-purity copper bar, which comprises the following steps: 1) crushing the copper ore to the diameter of less than or equal to 200mm to obtain crushed copper ore; 2) placing the crushed copper ores into a melting furnace, calcining at high temperature of 250-350 ℃, and taking out after preset time to obtain crushed materials; 3) putting the crushed materials into a sulfurous acid solution with the weight ratio of 1:2 for electrolytic leaching to obtain high-purity metal copper; 4) preparing copper rods from metal copper, putting the copper rods into an extruder, and continuously extruding for 3-5 times at the temperature of 350-550 ℃ to obtain copper bars; 5) and (4) cooling the copper bar in the step (4), and rolling and storing after cooling to normal temperature. According to the invention, the copper sulfide is converted into the copper oxide by high-temperature calcination, and then the metal copper is leached by point decomposition, so that the obtained metal copper has the highest weight, the utilization rate of the copper is improved, and more copper bars can be manufactured by the same weight of the copper ore.

Description

Preparation method of high-purity copper bar
Technical Field
The invention relates to the technical field of copper bar preparation, in particular to a preparation method of a high-purity copper bar.
Background
The copper bus is commonly called copper bar, and the copper bus is one of the main varieties of copper processing materials. The copper bus has high mechanical performance, good electrical conductivity and thermal conductivity, excellent corrosion resistance, electroplating property and brazing property, beautiful metal luster, good forming processability and the like, so that various power transmission and transformation, electric equipment and the like manufactured by the copper bus are widely applied to the field of electric power. In recent years, with the continuous high-speed development of national economy, the yield and consumption of copper buses in China are greatly improved, however, the utilization rate of copper in copper ores is not high, and the defects of internal air holes, shrinkage porosity and the like of the copper bars can occur in the existing copper bar manufacturing process.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing a high-purity copper bar.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a high-purity copper bar comprises the following steps:
1) crushing the copper ore to the diameter of less than or equal to 200mm to obtain crushed copper ore;
2) placing the crushed copper ores into a melting furnace, calcining at high temperature of 250-350 ℃, and taking out after preset time to obtain crushed materials;
3) putting the crushed materials into a sulfurous acid solution with the weight ratio of 1:2 for electrolytic leaching to obtain high-purity metal copper;
4) preparing copper rods from metal copper, putting the copper rods into an extruder, and continuously extruding for 3-5 times at the temperature of 350-550 ℃ to obtain copper bars;
5) and (4) cooling the copper bar in the step (4), cooling to normal temperature, rolling and storing, wherein the main components of the copper ore comprise copper oxide and copper sulfide, high-temperature calcination is utilized to decompose the copper sulfide into copper oxide and sulfur dioxide, the sulfur dioxide gas is recovered to avoid environmental pollution, the recovery method refers to the existing recovery process, the copper oxide is subjected to electrolytic leaching by a sulfurous acid solution to obtain high-purity copper, the high-purity copper is used for preparing a copper rod, the copper rod is extruded for multiple times to obtain the copper bar, and original internal casting defects of the copper rod, such as air holes, shrinkage porosity and the like, can be eliminated in the continuous extrusion process, so that the produced copper bus has fine grain size and compact internal organization.
Preferably, in the step 5, the temperature is cooled to 400 ℃ at a cooling speed of 5 ℃/s, then cooled to 400 ℃ at 250 ℃, then cooled to 250 ℃ at a cooling speed of 10 ℃/s, cooled to 250 ℃ at 100 ℃, then cooled to 250 ℃ at 100 ℃, and then cooled to normal temperature at a cooling speed of 8 ℃/s, the cooling process is divided into three stages, the cooling speed of each stage is different, and the mechanical performance of the copper bar can be increased by the method.
Preferably, in step 4, the finished copper rod is subjected to oil stain and deburring treatment which are remained during surface machining.
Preferably, the oil stain removing process comprises the steps of placing the copper rod in an oil removing groove, pouring an oil removing agent into the oil removing groove to remove oil from the copper rod, taking out the copper rod after 15-25 minutes, and cleaning the copper rod with clear water.
Preferably, the mass-to-volume ratio of the copper wire to the oil removing agent is 3: 1, the oil removing agent is a mixed solution of 3-5 parts of sodium nitrate, 5-8 parts of citric acid and 5-8 parts of tea saponin, the oil removing temperature is 30-60 ℃, the citric acid is a strong organic acid, can react with glycerol, is easy to dissolve in water and is convenient to clean after oil removal, the tea saponin belongs to triterpenoid saponin, is a non-ionic surfactant, and has good functions of emulsification, dispersion, foaming, moistening and the like.
Preferably, the calcination time is 1 to 2.5 hours.
Preferably, in the step 3, the leaching is carried out at normal temperature, and the leaching time is 25-45 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the copper sulfide is converted into copper oxide by high-temperature calcination, and then the metal copper is leached by point decomposition, so that the obtained metal copper has the highest weight, the utilization rate of the copper is improved, and more copper bars can be manufactured by the same weight of the copper ore;
2. through multiple times of extrusion, the defects of internal casting air holes and shrinkage porosity are reduced, and the tensile strength is improved;
3. the cooling processing is divided into three stages, the cooling speed of each stage is different, and the mechanical property of the copper bar can be improved by the method;
4. the nitrite is matched with the borate, so that the damage of pickling on the copper wire can be reduced while the oil removing agent is removed.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The invention provides a preparation method of a high-purity copper bar, which comprises the following steps:
1) crushing the copper ore to the diameter of less than or equal to 200mm to obtain crushed copper ore;
2) placing the crushed copper ores into a smelting furnace, calcining at high temperature of 250 ℃ for 1h, and taking out to obtain crushed materials;
3) putting the crushed materials into a sulfurous acid solution with the weight ratio of 1:2 for electrolytic leaching, and leaching at normal temperature for 25min to obtain high-purity metal copper;
4) preparing copper rods from metal copper, putting the copper rods into an extruder, and continuously extruding for 3 times at 350 ℃ to obtain copper bars;
5) and (4) cooling the copper bar in the step (4) to the normal temperature of 20 ℃ at the cooling speed of 5 ℃/s, and then rolling and storing.
Example 2
A preparation method of a high-purity copper bar comprises the following steps:
1) crushing the copper ore to the diameter of less than or equal to 200mm to obtain crushed copper ore;
2) placing the crushed copper ores into a smelting furnace, calcining at a high temperature of 300 ℃ for 2 hours, and taking out to obtain crushed materials;
3) putting the crushed materials into a sulfurous acid solution with the weight ratio of 1:2 for electrolytic leaching, and leaching at normal temperature for 30min to obtain high-purity metal copper;
4) preparing copper rods from metal copper, putting the copper rods into an extruder, and continuously extruding for 4 times at the temperature of 450 ℃ to obtain copper bars;
5) and (4) cooling the copper bar in the step (4) to the normal temperature of 20 ℃ at the cooling speed of 5 ℃/s, and then rolling and storing.
Example 3
A preparation method of a high-purity copper bar comprises the following steps:
1) crushing the copper ore to the diameter of less than or equal to 200mm to obtain crushed copper ore;
2) placing the crushed copper ores into a melting furnace, calcining at high temperature of 350 ℃ for 2.5 hours, and taking out to obtain crushed materials;
3) putting the crushed materials into a sulfurous acid solution with the weight ratio of 1:2 for electrolytic leaching, and leaching at normal temperature for 45min to obtain high-purity metal copper;
4) preparing copper rods from metal copper, putting the copper rods into an extruder, and continuously extruding for 5 times at 550 ℃ to obtain copper bars;
5) and (4) cooling the copper bar in the step (4) to the normal temperature of 20 ℃ at the cooling speed of 5 ℃/s, and then rolling and storing.
Comparative example 1
A high-purity copper bar preparation method comprises the steps of crushing copper ore to the diameter of less than or equal to 200mm to obtain crushed copper ore, precipitating copper sulfide in the crushed copper ore by adopting a sodium sulfide precipitation method at 82 ℃ to obtain copper concentrate, placing the copper concentrate into ethanol for replacement by utilizing a reduction reaction to obtain metal copper, manufacturing the metal copper into a copper rod, placing the copper rod into an extruder, extruding at 300 ℃, and then drawing and annealing to obtain the copper bar.
Copper bars obtained by the methods of example 1, example 2, example 3 and comparative example 1 are respectively compared with the same batch of copper ores with the same weight, and specific data are shown in table 1;
TABLE 1
Figure BDA0003002926720000031
Figure BDA0003002926720000041
Table 1 shows that, in the embodiment 3, as an optimal scheme, after copper sulfide is converted into copper oxide by high-temperature calcination, metallic copper is leached by point decomposition, the obtained metallic copper has the highest weight, the utilization rate of copper is improved, more copper bars can be manufactured by the same weight of copper ore, internal casting defects such as air holes and shrinkage porosity defects are reduced by multiple times of extrusion, and the tensile strength is improved.
Example 4
This embodiment is substantially the same as embodiment 3 except that:
the cooling treatment is to cool the copper bar to 300 ℃ at a cooling speed of 5 ℃/s, cool the copper bar to 300 ℃, cool the copper bar to 200 ℃ at a cooling speed of 10 ℃/s, cool the copper bar to 20 ℃ at a cooling speed of 8 ℃/s, cool the copper bar to normal temperature (20 ℃) at a cooling speed of 200 ℃, and divide the cooling processing into three stages, wherein the cooling speeds of the stages are different, and the mechanical property of the copper bar can be improved by the method.
The tensile strength of the copper bars prepared by the methods of example 3 and example 4 were compared, and the specific data are shown in table 2;
TABLE 2
Example 3 Example 4
Tensile strength/Ma 283 304
It can be known from table 2 that the cooling treatment is divided into three stages, and the cooling rate in each stage is different, reduces the residual stress, and reduces deformation and crack tendency while stabilizing the size, increases the tensile strength of the copper bar.
Example 5
This embodiment is substantially the same as embodiment 4 except that:
in step 4, before the copper rod is placed into the extruding machine, the surface of the manufactured copper rod is subjected to oil stain removal and deburring treatment.
The oil stain removing process comprises the following steps:
placing the copper rod in an oil removing groove, pouring an oil removing agent into the oil removing groove to carry out an oil removing process on the copper rod, fishing out after 19 minutes, cleaning with clear water, wherein the solid-liquid mass-volume ratio of the copper wire to the oil removing agent is 3: the degreasing agent is a mixed solution of 3 parts of sodium nitrate, 6 parts of citric acid and 6 parts of tea saponin, the degreasing temperature is 45 ℃, a corrosion inhibitor needs to be added due to the fact that acid has a large corrosion effect on metal, the decontamination effect of borate is strong, and the nitrite is matched with the borate, so that the damage of pickling on a copper rod can be reduced while the degreasing agent is removed.
As is clear from the observation of the surface of the copper bar, the gloss of the copper bar in example 2 was inferior to that of example 5, and rust was present in a part of the copper bar in example 2, and after the copper bar in example 2 was washed with clear water, a water-insoluble residual liquid was also visible to the naked eye, and neither rust nor residual liquid was found in example 5.
Comparative example 2
An oil removing agent comprises 20 parts of sodium bicarbonate, 20 parts of surfactant, 35 parts of alkylphenol polyoxyethylene and 45 parts of ionized water.
The oil removing agent component in the embodiment 5 is replaced by the component in the comparative example 2, the copper rod is simultaneously degreased, and the surface of the degreased copper rod is observed, so that the glossiness of the copper rod in the comparative example 2 is inferior to that in the embodiment 5, the comparative example 2 has no obvious rust mark, but the residual liquid insoluble in water can be seen by naked eyes after the copper rod is cleaned by clear water, and therefore, the oil removing effect of the embodiment is better.
The above additional technical features can be freely combined and used in superposition by those skilled in the art without conflict.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the patent and protection scope of the present invention should be subject to the appended claims.

Claims (7)

1. A preparation method of a high-purity copper bar is characterized by comprising the following steps:
1) crushing the copper ore to the diameter of less than or equal to 200mm to obtain crushed copper ore;
2) placing the crushed copper ores into a melting furnace, calcining at high temperature of 250-350 ℃, and taking out after preset time to obtain crushed materials;
3) putting the crushed materials into a sulfurous acid solution with the weight ratio of 1:2 for electrolytic leaching to obtain high-purity metal copper;
4) preparing copper rods from metal copper, putting the copper rods into an extruder, and continuously extruding for 3-5 times at the temperature of 350-550 ℃ to obtain copper bars;
5) and (4) cooling the copper bar in the step (4), and rolling and storing after cooling to normal temperature.
2. The method as claimed in claim 1, wherein in the step 5, the cooling process is performed by cooling the temperature to 400 ℃ at a cooling rate of 5 ℃/s, cooling to 400 ℃ at 250-.
3. The method for manufacturing a high-purity copper bar as claimed in claim 1, wherein in the step 4, the manufactured copper bar is subjected to oil stain and deburring treatment which are remained during surface processing.
4. The method for preparing the high-purity copper bar as claimed in claim 2, wherein the oil stain removing process comprises placing the copper bar in an oil removing tank, pouring an oil removing agent into the oil removing tank to remove oil from the copper bar, and taking out the copper bar after 15-25 minutes and cleaning the copper bar with clean water.
5. The method for preparing the high-purity copper bar as claimed in claim 4, wherein the solid-liquid mass-volume ratio of the copper bar to the oil remover is 3: 1, the oil removing agent is a mixed solution of 3-5 parts of sodium nitrate, 5-8 parts of citric acid and 5-8 parts of tea saponin, and the oil removing temperature is 30-60 ℃.
6. The method for preparing a high-purity copper bar as claimed in claim 1, wherein the calcination time is 1-2.5 h.
7. The method for preparing a high-purity copper bar as claimed in claim 1, wherein in the step 3, the electrolytic leaching is performed at normal temperature, and the leaching time is 25-45 min.
CN202110353852.9A 2021-04-01 2021-04-01 Preparation method of high-purity copper bar Pending CN113096884A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB191100100A (en) * 1911-01-02 1912-01-02 Lionel Ernest Bussey Improvements relating to the Extraction of Copper from Ores containing that Metal.
GB238962A (en) * 1924-05-29 1925-08-31 Henry Squarebrigs Mackay Improvements in or relating to the electro-chemical treatment of copper ores
CN1084585A (en) * 1993-08-10 1994-03-30 李学刚 Process for one-stage electrolytic extraction of copper
CN103962409A (en) * 2014-05-20 2014-08-06 王国华 Manufacturing method of copper wire
CN105107862A (en) * 2015-09-24 2015-12-02 云南新铜人实业有限公司 Copper bar continuous extrusion short process production method
CN111197171A (en) * 2020-02-18 2020-05-26 华建彬 Wet copper extraction process
CN112280942A (en) * 2020-09-01 2021-01-29 山西太钢不锈钢股份有限公司 Martensitic stainless steel 2Cr13 wire annealing process

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB191100100A (en) * 1911-01-02 1912-01-02 Lionel Ernest Bussey Improvements relating to the Extraction of Copper from Ores containing that Metal.
GB238962A (en) * 1924-05-29 1925-08-31 Henry Squarebrigs Mackay Improvements in or relating to the electro-chemical treatment of copper ores
CN1084585A (en) * 1993-08-10 1994-03-30 李学刚 Process for one-stage electrolytic extraction of copper
CN103962409A (en) * 2014-05-20 2014-08-06 王国华 Manufacturing method of copper wire
CN105107862A (en) * 2015-09-24 2015-12-02 云南新铜人实业有限公司 Copper bar continuous extrusion short process production method
CN111197171A (en) * 2020-02-18 2020-05-26 华建彬 Wet copper extraction process
CN112280942A (en) * 2020-09-01 2021-01-29 山西太钢不锈钢股份有限公司 Martensitic stainless steel 2Cr13 wire annealing process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
黄礼煌: "《化学选矿》", 30 April 2012 *

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Application publication date: 20210709