CN111519055A - Preparation method of high-copper-content red impure copper - Google Patents
Preparation method of high-copper-content red impure copper Download PDFInfo
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- CN111519055A CN111519055A CN202010400788.0A CN202010400788A CN111519055A CN 111519055 A CN111519055 A CN 111519055A CN 202010400788 A CN202010400788 A CN 202010400788A CN 111519055 A CN111519055 A CN 111519055A
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- copper
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- heat preservation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
Abstract
A method for preparing red impure copper with high copper content, according to the application and smelting production process of red impure copper; firstly, melting raw materials of red impure copper in an induction furnace, then adding pure copper to smelt a copper melt, transferring the copper melt to a heat preservation furnace for 5-10 minutes, and adding a proper amount of Cu-P intermediate alloy into the melt; before the solution enters the heat preservation, a proper amount of Cu-RE intermediate alloy is put into a heat preservation furnace; pouring all the melt into a heat preservation furnace, adding phosphorus copper accounting for 1-5% of the mass of the alloy liquid into the melt for deoxidation, adding a refining slag former to complete primary refining, and blowing nitrogen into the copper melt; and after fully slagging off the copper melt, carrying out copper liquid reduction, standing for 40-80 minutes, and starting casting. The copper content of the molten copper produced by the secondary refining process reaches 99.3 percent (by mass percentage) or more, and the method has the advantages of high production efficiency, low investment, low energy consumption, simple production process, low production cost and little environmental pollution.
Description
Technical Field
The invention relates to the technical field of nonferrous metals, in particular to a preparation method of red impure copper with high copper content.
Background
Copper is the basic material for national economic development. Along with the annual increase of the economy of China, the demand of various industries on copper is increased, and the copper ore resources of China are gradually deficient and the ore grade is continuously reduced, so that the recycling and reutilization of waste copper are particularly important.
The red impure copper is scrap copper with the copper content of not less than 90 percent, and contains various harmful impurity elements, such as Ni and the like, which are dissolved into the metal to remarkably reduce the conductive performance of the copper, while non-dissolved impurities such as O, S and the like often form eutectic or brittle compounds with the copper to reduce the plasticity of the alloy, and the elements often bring adverse effects on the subsequent processing and use performance of the copper alloy. Most of the red impure copper is recovered in the forms of remelting, refining, electrolysis and the like, and the waste copper wire with better quality can be directly used for processing various wire rods. The recovery and utilization of the waste copper are mainly divided into two types, the first type is direct utilization, namely high-quality impure copper is refined into pure copper or copper alloy which accounts for 2/3 of the total amount of the waste copper; the second type is indirect utilization, i.e. base metal impurities in scrap copper are removed by smelting, usually by electrorefining, 1/3 which accounts for the total amount of scrap copper. The direct utilization saves energy by 50 percent compared with the electrolytic purification, and avoids the environmental pollution.
In the production process of the red impure copper, the converter modes which are commonly used include a tilting converter, an overflow converter and a submerged converter. The launder of the overflow converter needs to ensure a certain temperature and is additionally provided with a melt protection measure, the investment of the undercurrent converter is large, the running cost is high, and the tilting converter is adopted by a plurality of small and medium-sized enterprises as a converter mode which has low cost, high efficiency and can produce discontinuously. The mode is mainly characterized in that a melt enters the holding furnace through a copper outlet and a launder by the rotation of the smelting furnace, and even the copper melt is directly poured into the holding furnace. In the mode of separation of the smelting furnace and the holding furnace, the problem of unstable melt quality exists, because the copper melt cannot be sealed when being dumped and transferred, oxygen and hydrogen which absorb air are easily caused, and various situations of oxidation slag inclusion and the like are formed, so that the quality defects of the cast ingot are caused, particularly, the number of internal air holes is large, the density of the cast ingot is low, and the copper content is low.
The applicant has therefore developed, through long-term practice, a process for the preparation of impure red copper with an increased copper content.
Disclosure of Invention
The invention aims to provide a preparation method of red impure copper with high copper content, which effectively reduces the loss of nutrient components. The dissolution of small molecular substances on the surface of the inner layer can be reduced during cooking, and the nutrient loss during cooking is reduced; the product of the invention can meet the nutritional requirements of growth and development of children, can meet the actual production, and has the characteristics of good taste, low cooking loss rate and the like.
The purpose of the invention is realized by the following technical scheme: a method for preparing red impure copper with high copper content,
1) carrying out assay analysis on the red impure copper to be melted to determine the copper content;
2) according to the analysis result, removing impurity metal elements in the red impure copper according to the procedures of charging, melting, oxidizing, degassing, slagging, deslagging, reducing and refining;
3) according to the application and smelting production process of the red impure copper; firstly, melting raw materials of red impure copper in an induction furnace, then adding pure copper to smelt a copper melt, transferring the copper melt to a heat preservation furnace for 5-10 minutes, and adding a proper amount of Cu-P intermediate alloy into the melt; before the solution enters the heat preservation, a proper amount of Cu-RE intermediate alloy is put into a heat preservation furnace; pouring all the melt into a heat preservation furnace, adding phosphorus copper accounting for 1-5% of the mass of the alloy liquid into the melt for deoxidation, adding a refining slag former to complete primary refining, and blowing nitrogen into the copper melt; and after fully slagging off the copper melt, carrying out copper liquid reduction, standing for 40-80 minutes, and starting casting.
As a preferred technical scheme: the addition amount of the pure copper is 0.2 time of the content of the red impure copper solution.
As a preferred technical scheme: covering the mixture by using graphite, carbon powder and wood dust; the temperature of the copper liquid is controlled between 1000 ℃ and 1400 ℃ when the reduction is finished.
As a preferred technical scheme: blowing nitrogen into the copper melt, wherein the nitrogen takes high-purity N2 as a carrier, and the refining slag former comprises CaCO 3, NaCl and SiO 2, blowing the nitrogen into the copper liquid, wherein the CaCO, NaCl and SiO are mixed according to the proportion of 1:1:1.5, the refining time is 10-15 minutes, and the temperature of the copper liquid is ensured to be between 1200 and 1400 ℃ in the refining process; and after the refining process is finished, standing the copper liquid for 8-10 minutes.
As a preferred technical scheme: the refining process comprises primary refining and secondary refining, wherein different refining agents are used for the primary refining and the secondary refining, the refining agent consisting of cryolite, salt and sodium fluoride is used for refining the copper liquid, the cryolite, the salt and the sodium fluoride are proportioned according to the proportion of 1:2:0.5, the using amount is 0.3% -0.6%, and the refining method is that the refining agent is blown into the copper liquid by taking high-purity N2 as a carrier under the condition that the first refining pressure is lower than the first refining pressure.
As a preferred technical scheme: the Cu-RE intermediate alloy is added into the heat preserving furnace, and the addition amount of the rare earth element in the Cu-RE intermediate alloy is 0.03-0.07 percent of the mass of the copper melt.
As a preferred technical scheme: the refining slagging agent also comprises borax, wherein the addition amount of the borax is 0.05-0.07% of the melt quality.
As a preferred technical scheme: and pouring the melt into a heat preservation furnace, fully slagging off, covering by covering a mixture of graphite, carbon powder and wood dust, standing for 30-45 minutes, and starting casting.
Compared with the prior art, the invention has the beneficial effects that: the method ensures the full implementation of impurity removal and degassing in the refining process, overcomes the problems of strong gas absorption of red copper and poor sealing performance in the casting process, has strong refining capability, obviously improves the density of cast ingots, and has obvious effect of improving the quality of red impure copper products.
(2) The refining method has low energy consumption, and the adopted raw materials are cheap and easy to obtain; the method can well wet the furnace lining, does not react with the furnace lining to damage equipment, and forms a melt with proper viscosity and surface tension; the flux used can form a protective layer and can be easily separated from the melt.
(3) The copper content of the molten copper produced by the secondary refining process reaches 99.3 percent (by mass percentage) or more, and the production efficiency is high.
(4) Has the advantages of low investment, low energy consumption, simple production process, low production cost and little environmental pollution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
A method for preparing red impure copper with high copper content,
1) carrying out assay analysis on the red impure copper to be melted to determine the copper content;
2) according to the analysis result, removing impurity metal elements in the red impure copper according to the procedures of charging, melting, oxidizing, degassing, slagging, deslagging, reducing and refining;
3) according to the application and smelting production process of the red impure copper; firstly, melting raw materials of red impure copper in an induction furnace, then adding pure copper to smelt a copper melt, transferring the copper melt to a heat preservation furnace for 5-10 minutes, and adding a proper amount of Cu-P intermediate alloy into the melt; before the solution enters the heat preservation, a proper amount of Cu-RE intermediate alloy is put into a heat preservation furnace; pouring all the melt into a heat preservation furnace, adding phosphorus copper accounting for 1-5% of the mass of the alloy liquid into the melt for deoxidation, adding a refining slag former to complete primary refining, and blowing nitrogen into the copper melt; and after fully slagging off the copper melt, carrying out copper liquid reduction, standing for 40-80 minutes, and starting casting.
In this example, the amount of pure copper added was 0.2 times the amount of the impure copper solution.
In this example, a mixture of graphite and carbon powder plus wood chips is used to cover the substrate; the temperature of the copper liquid is controlled between 1000 ℃ and 1400 ℃ when the reduction is finished.
In the embodiment, nitrogen is blown into the copper melt, wherein the nitrogen uses high-purity N2 as a carrier, the refining slagging agent comprises CaCO 3, NaCl and SiO 2, and is blown into the copper liquid, wherein the mixture of the CaCO, the NaCl and the SiO is mixed according to the proportion of 1:1:1.5, the refining time is 10-15 minutes, and the temperature of the copper liquid is ensured to be between 1200 and 1400 ℃ in the refining process; and after the refining process is finished, standing the copper liquid for 8-10 minutes.
In the embodiment, the refining process is divided into primary refining and secondary refining, different refining agents are used for two times, the secondary refining is used for refining the copper liquid by using the refining agent consisting of cryolite, salt and sodium fluoride, the cryolite, the salt and the sodium fluoride are proportioned according to the proportion of 1:2:0.5, the using amount is 0.3% -0.6%, and the refining method is that the refining agent is blown into the copper liquid by using high-purity N2 as a carrier under the condition that the pressure is less than the first refining pressure.
In this example, the amount of the added Cu-RE intermediate alloy in the holding furnace is such that the rare earth element therein is 0.03-0.07% of the mass of the copper melt.
In this embodiment, the refining slag former further comprises borax, wherein the addition amount of the borax is 0.05-0.07% of the melt quality.
In the embodiment, after the melt is poured into a holding furnace, the melt is fully skimmed, covered by a covering mixture of graphite, carbon powder and wood dust, and kept stand for 30-45 minutes to start casting.
Example 1: melting raw materials of the red impure copper in an induction furnace, adding pure copper, pouring the pure copper in each furnace, transferring the pure copper to the front of a heat preservation furnace for 10 minutes, and adding Cu-7P intermediate alloy into a melt; before the copper melt is poured and transferred into a holding furnace, putting the Cu-RE intermediate alloy with the mass being one third of that of the Cu-7P intermediate alloy into the holding furnace; after all the melt is poured into a heat preservation furnace each time, fully dehydrating and drying primary refining agents CaCO 3, NaCl, SiO 2 and borax which take the Cu-7P intermediate alloy as one half, and blowing nitrogen into the copper melt; fully slagging off the copper melt after pouring and refining each time, standing for 15 minutes, mixing secondary refining agents of cryolite, salt and sodium fluoride with the same mass as the primary refining agents, blowing nitrogen into the copper melt, covering with a covering mixture of graphite, carbon powder and wood dust, standing for 25 minutes, and then starting horizontal continuous casting to obtain an ingot with the diameter of 170 mm. The ingot was sawn into specified lengths and weighed to give an ingot density of 9.80g/cm 2, indicating a higher ingot density.
Example 2: melting raw materials of the red impure copper in an induction furnace, adding pure copper, pouring each furnace and transferring the materials to a heat preservation furnace for 6 minutes, and adding 2 kg/ton of Cu-10P intermediate alloy into a melt; before the copper melt is poured and transferred into a holding furnace, 0.1 kg/ton of Cu-RE intermediate alloy is put into the holding furnace; after all the melt is poured into a holding furnace each time, blowing 1 kg/ton of fully dehydrated and dried primary refining agent into the copper melt by adopting nitrogen; fully slagging off the copper melt after pouring and refining each time, standing for 15 minutes, mixing secondary refining agents of cryolite, salt and sodium fluoride with the same mass as the primary refining agents, blowing nitrogen into the copper melt, covering with a covering mixture of graphite, carbon powder and wood dust, and horizontally and continuously casting after 30 minutes to obtain an ingot with the diameter of 155 mm. The ingot was sawn into specified lengths and weighed to give an ingot density of 9.72g/cm 2, indicating a higher ingot density.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A method for preparing red impure copper with high copper content is characterized in that:
1) carrying out assay analysis on the red impure copper to be melted to determine the copper content;
2) according to the analysis result, removing impurity metal elements in the red impure copper according to the procedures of charging, melting, oxidizing, degassing, slagging, deslagging, reducing and refining;
3) according to the application and smelting production process of the red impure copper; firstly, melting raw materials of red impure copper in an induction furnace, then adding pure copper to smelt a copper melt, transferring the copper melt to a heat preservation furnace for 5-10 minutes, and adding a proper amount of Cu-P intermediate alloy into the melt; before the solution enters the heat preservation, a proper amount of Cu-RE intermediate alloy is put into a heat preservation furnace; pouring all the melt into a heat preservation furnace, adding phosphorus copper accounting for 1-5% of the mass of the alloy liquid into the melt for deoxidation, adding a refining slag former to complete primary refining, and blowing nitrogen into the copper melt; and after fully slagging off the copper melt, carrying out copper liquid reduction, standing for 40-80 minutes, and starting casting.
2. The method for refining red impure copper by tilting casting according to claim 1, characterized in that: the addition amount of the pure copper is 0.2 time of the content of the red impure copper solution.
3. The method for refining red impure copper by tilting casting according to claim 1, characterized in that: covering the mixture by using graphite, carbon powder and wood dust; the temperature of the copper liquid is controlled between 1000 ℃ and 1400 ℃ when the reduction is finished.
4. The method for preparing red impure copper with high copper content according to claim 1, which is characterized in that: blowing nitrogen into the copper melt, wherein the nitrogen takes high-purity N2 as a carrier, and the refining slag former comprises CaCO 3, NaCl and SiO 2, blowing the nitrogen into the copper liquid, wherein the CaCO, NaCl and SiO are mixed according to the proportion of 1:1:1.5, the refining time is 10-15 minutes, and the temperature of the copper liquid is ensured to be between 1200 and 1400 ℃ in the refining process; and after the refining process is finished, standing the copper liquid for 8-10 minutes.
5. The method for preparing red impure copper with high copper content according to claim 1, which is characterized in that: the refining process comprises primary refining and secondary refining, wherein different refining agents are used for the primary refining and the secondary refining, the refining agent consisting of cryolite, salt and sodium fluoride is used for refining the copper liquid, the cryolite, the salt and the sodium fluoride are proportioned according to the proportion of 1:2:0.5, the using amount is 0.3% -0.6%, and the refining method is that the refining agent is blown into the copper liquid by taking high-purity N2 as a carrier under the condition that the first refining pressure is lower than the first refining pressure.
6. The method for refining red impure copper by tilting casting according to claim 1, characterized in that: the Cu-RE intermediate alloy is added into the heat preserving furnace, and the addition amount of the rare earth element in the Cu-RE intermediate alloy is 0.03-0.07 percent of the mass of the copper melt.
7. The method for refining red impure copper by tilting casting according to claim 1, characterized in that: the refining slagging agent also comprises borax, wherein the addition amount of the borax is 0.05-0.07% of the melt quality.
8. The method for refining red impure copper by tilting casting according to claim 1, characterized in that: and pouring the melt into a heat preservation furnace, fully slagging off, covering by covering a mixture of graphite, carbon powder and wood dust, standing for 30-45 minutes, and starting casting.
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| CN202010400788.0A CN111519055A (en) | 2020-05-13 | 2020-05-13 | Preparation method of high-copper-content red impure copper |
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| CN202010400788.0A CN111519055A (en) | 2020-05-13 | 2020-05-13 | Preparation method of high-copper-content red impure copper |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB409910A (en) * | 1932-06-06 | 1934-05-10 | Electro Chimie Metal | Process for refining crude copper |
| CN102433438A (en) * | 2011-12-16 | 2012-05-02 | 金川集团有限公司 | Treatment method of scrap copper |
| CN103725897A (en) * | 2013-12-27 | 2014-04-16 | 中南大学 | Method for directly producing high-purity oxygen-free copper by pyrogenic process continuous refining of scrap copper |
| CN105603201A (en) * | 2016-03-21 | 2016-05-25 | 江西保太有色金属集团有限公司 | Impure red copper refining method through dumping, transferring, melting and casting |
| CN106086445A (en) * | 2016-08-10 | 2016-11-09 | 安徽晋源铜业有限公司 | A kind of cleaning molten method of oxygen-free copper bar |
| CN108220620A (en) * | 2017-12-31 | 2018-06-29 | 安徽晋源铜业有限公司 | A kind of copper scap refinery practice |
-
2020
- 2020-05-13 CN CN202010400788.0A patent/CN111519055A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB409910A (en) * | 1932-06-06 | 1934-05-10 | Electro Chimie Metal | Process for refining crude copper |
| CN102433438A (en) * | 2011-12-16 | 2012-05-02 | 金川集团有限公司 | Treatment method of scrap copper |
| CN103725897A (en) * | 2013-12-27 | 2014-04-16 | 中南大学 | Method for directly producing high-purity oxygen-free copper by pyrogenic process continuous refining of scrap copper |
| CN105603201A (en) * | 2016-03-21 | 2016-05-25 | 江西保太有色金属集团有限公司 | Impure red copper refining method through dumping, transferring, melting and casting |
| CN106086445A (en) * | 2016-08-10 | 2016-11-09 | 安徽晋源铜业有限公司 | A kind of cleaning molten method of oxygen-free copper bar |
| CN108220620A (en) * | 2017-12-31 | 2018-06-29 | 安徽晋源铜业有限公司 | A kind of copper scap refinery practice |
Non-Patent Citations (1)
| Title |
|---|
| 陈琦 等: "《铸件配料手册》", 30 April 2000, 机械工业出版社 * |
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