CN114717413A - Copper smelting process for soaking waste copper material by high-pressure oxygen - Google Patents
Copper smelting process for soaking waste copper material by high-pressure oxygen Download PDFInfo
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- CN114717413A CN114717413A CN202210497509.6A CN202210497509A CN114717413A CN 114717413 A CN114717413 A CN 114717413A CN 202210497509 A CN202210497509 A CN 202210497509A CN 114717413 A CN114717413 A CN 114717413A
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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
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
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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
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to a high-pressure oxygen soaking treatment copper smelting process for a waste copper material, which sequentially cleans dust impurities on the waste copper material, cleans oil stains on the waste copper material, polishes stubborn oxides and impurities on the waste copper material, and removes an oxide film on the waste copper material. And crushing the waste copper material into particles so as to fully convert the copper simple substance into 2-valent copper ions. In the process, the leachate containing 2-valent copper ions is not directly electrolyzed, but part of waste copper particles are used for converting the 2-valent copper ions in the leachate into 1-valent copper ions. And then carrying out electrolytic treatment on the electrolyte containing 1-valent copper ions to obtain cathode copper. By adopting the mode, on one hand, more waste copper particles can be treated, the production cost is reduced, the production efficiency is improved, on the other hand, the efficiency of electrolyzing the electrolyte containing 1-valent copper ions is higher, and the production efficiency is further improved. The copper smelting process for the high-pressure oxygen soaking treatment of the waste copper material has low cost and high efficiency.
Description
Technical Field
The invention relates to the field of copper smelting, in particular to a copper smelting process for soaking waste copper materials by high-pressure oxygen.
Background
Copper ore mined from copper ore is subjected to ore dressing to become copper concentrate or copper ore sand with higher copper-containing grade, and the copper concentrate can become refined copper and copper products only after being smelted and extracted. The development of copper metallurgy technology goes through a long process, but the copper smelting is mainly carried out by a fire method until now, the output of the copper smelting accounts for about 85 percent of the world copper output, the modern wet smelting technology is gradually popularized, and the smelting cost of the copper is greatly reduced by the popularization of the wet smelting, so that the copper smelting technology is adopted by mass production manufacturers more and more. The economic development mode of recycling renewable resources and continuously recycling materials is becoming a global trend. The strategy of sustainable development is agreed by everyone. Sustainable development is development which not only meets the requirements of contemporary human beings, but also does not damage the ability of the latter to meet the requirements, and is the quantity of economic growth which we pay attention to, but also pursue the quality of economic growth. The main sign is that the resources can be utilized forever, and good ecological environment is kept.
However, for the copper smelting field, besides copper concentrate, the waste copper is also the main raw material for refining copper, including old waste copper and new waste copper, the old waste copper comes from old equipment and old machines, abandoned buildings and underground pipelines; the new copper scrap comes from copper scrap discarded by processing plants, generally the copper scrap is supplied more stably, and the copper produced from the copper scrap and other similar materials is also called reclaimed copper. The traditional process for recovering and refining the waste copper has high cost and low efficiency and cannot meet the production requirement.
Disclosure of Invention
Therefore, the copper smelting process for soaking the waste copper material by high pressure oxygen is needed to solve the technical problems that the traditional process for recovering and refining the waste copper is high in cost, low in efficiency and incapable of meeting production requirements.
A copper smelting process for high-pressure oxygen soaking treatment of waste copper materials comprises the following steps:
oil stain removal: cleaning the surface of the waste copper material with clear water, drying, and soaking the waste copper material in deoiling liquid for cleaning and deoiling after drying;
surface cleaning: cleaning the surface of the deoiled waste copper material with clear water, polishing, cleaning with clear water after polishing, and drying after cleaning;
removing the oxide film: soaking the dried waste copper material in a pickling solution to remove an oxide film on the surface;
crushing the waste copper material: crushing the waste copper material into particles;
a high-pressure oxygen leaching step: placing part of the waste copper material particles into a soaking solution, pressurizing and introducing oxygen, and filtering material residues to obtain a leaching solution after full reaction;
a reduction reaction step: placing part of waste copper material particles into the leaching solution for full reaction, and filtering material residues to obtain electrolyte;
a rotational flow electrolysis step: and carrying out cyclone electrolysis treatment on the obtained electrolyte to obtain cathode copper.
In one embodiment, the scrap copper particles are continuously stirred during the hyperbaric oxygen leaching step.
In one embodiment, in the hyperbaric oxygen leaching step, the hyperbaric oxygen leaching process is completed in a autoclave.
In one embodiment, the waste copper particles are continuously stirred during the reduction step.
In one embodiment, the soaking solution contains copper chloride, sodium chloride and calcium chloride, wherein the concentration of the copper chloride is 54g/L-110g/L, the concentration of the sodium chloride is 220g/L-270g/L, and the concentration of the calcium chloride is 220g/L-270 g/L.
In one embodiment, in the reduction step, the PH of the leachate is adjusted to 4.5 to 4.8 using a PH adjuster.
In one embodiment, in the high pressure oxygen leaching step, the mass of the soaking solution is 12 times to 16 times the mass of a part of the waste copper material particles.
In one embodiment, in the hyperbaric oxygen leaching step, the reaction temperature is 115 to 120 degrees celsius.
In one embodiment, in the high pressure oxygen leaching step, the oxygen pressure is 0.6 to 0.8 MPa.
In one embodiment, in the reduction reaction step, the mass of the soaking solution is 12 times to 16 times that of a part of the waste copper material particles.
The copper smelting process for soaking the waste copper material by using the high-pressure oxygen comprises the steps of sequentially cleaning dust impurities on the waste copper material, cleaning oil stains on the waste copper material, polishing stubborn oxides and impurities on the waste copper material, and removing an oxide film on the waste copper material. And crushing the waste copper material into particles so as to fully convert the copper simple substance into 2-valent copper ions. It is emphasized that in the present process, the leachate containing copper ions of value 2 is not directly subjected to electrolysis, but rather, a portion of the copper scrap particles is used to convert the copper ions of value 2 in the leachate to copper ions of value 1. And then carrying out electrolysis treatment on the electrolyte containing the 1-valent copper ions to obtain cathode copper. By adopting the mode, on one hand, more waste copper particles can be treated, the production cost is reduced, the production efficiency is improved, on the other hand, the efficiency of electrolyzing the electrolyte containing 1-valent copper ions is higher, and the production efficiency is further improved. The copper smelting process for the high-pressure oxygen soaking treatment of the waste copper materials has the advantages of low cost and high efficiency, and can meet production requirements.
Drawings
FIG. 1 is a schematic flow chart of a copper smelting process by high-pressure oxygen soaking treatment of a waste copper material in one embodiment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Referring to fig. 1, the invention provides a copper smelting process for high-pressure oxygen soaking treatment of waste copper materials, which comprises the following steps:
step 101: oil stain removal: and (3) cleaning the surface of the waste copper material with clear water, drying, and soaking the waste copper material in degreasing liquid for cleaning and degreasing after drying.
Specifically, the surface of the waste copper material is cleaned by clear water to remove dust and impurities adhered to the surface of the waste copper material. In this embodiment, in the step of removing the oil stain, the waste copper material is cleaned with clear water by using ultrasonic cleaning, so as to improve the cleaning effect on dust and impurities and improve the cleaning efficiency. And after the dust and impurities are removed, drying. And after drying, placing the waste copper material in degreasing liquid for soaking, cleaning and degreasing so as to remove oil stains on the surface of the waste copper material. In this embodiment, in the oil stain removing step, the waste copper material is placed in the deoiling liquid to be soaked, cleaned and deoiled, and ultrasonic cleaning is adopted. So as to improve the cleaning effect of the oil stain and improve the cleaning efficiency of the oil stain. In this example, the degreasing fluid contains hydrochloric acid, hydroxyethylidene diphosphonic acid, a hyperbranched polymer, and polyethylene oxide. The concentration of the hydrochloric acid is 50g/L-150g/L, the concentration of the hydroxyethylidene diphosphonic acid is 80g/L-120g/L, the concentration of the hyperbranched polymer is 4g/L-8g/L, and the concentration of the polyoxyethylene is 4g/L-6 g/L. The oil removing liquid has high oil outlet effect and high efficiency.
Step 102: surface cleaning: and cleaning the surface of the deoiled waste copper material with clear water, polishing, cleaning with clear water after polishing, and drying after cleaning.
Specifically, the deoiling liquid on the surface of the waste copper material is removed after the surface of the deoiled waste copper material is cleaned by clear water. And then polishing the surface of the waste copper material to remove a stubborn oxide layer on the surface of the waste copper material and adhered stubborn impurity foreign matters. And cleaning the polished workpiece with clean water to remove powder impurities. And (5) drying after cleaning. In this embodiment, in the surface cleaning step, ultrasonic cleaning is adopted in the process of cleaning the waste copper material with clean water, so as to rapidly, effectively and thoroughly remove the degreasing liquid and the powder impurities.
Step 103: removing the oxide film: and soaking the dried waste copper material in a pickling solution to remove the oxide film on the surface.
Specifically, the dried waste copper material is soaked in a pickling solution to remove an oxide film on the surface. In one embodiment, the pickling solution contains sulfuric acid, glycolic acid, methyl acrylate, sodium persulfate and ammonium persulfate, wherein the concentration of the sulfuric acid is 20g/L-50g/L, the concentration of the glycolic acid is 30g/L-60g/L, the concentration of the sodium persulfate is 50g/L-80g/L, and the concentration of the ammonium persulfate is 60g/L-90g/L and 2g/L-3 g/L. The pickling solution has moderate corrosivity, and avoids excessive corrosion of the waste copper material and copper resource waste on the basis of ensuring that the oxide film on the surface of the waste copper material is removed.
Step 104: crushing the waste copper material: and crushing the waste copper material into particles.
Specifically, the waste copper material is pulverized into particles by a metal pulverizer, and in one embodiment, in the step of pulverizing the waste copper material, the waste copper material is pulverized into particles with a maximum width of not more than 10 mm. So as to facilitate subsequent rapid and effective dissolution.
Step 105: a high-pressure oxygen leaching step: and (3) placing part of the waste copper material particles into a soaking solution, pressurizing and introducing oxygen, fully reacting, and filtering out material residues to obtain a leaching solution.
Specifically, a part of waste copper material particles are placed in a soaking solution, oxygen is introduced under pressure, and after full reaction, material residues are filtered to obtain a leaching solution. In the embodiment, the soaking solution contains copper chloride, sodium chloride and calcium chloride, wherein the concentration of the copper chloride is 54g/L-110g/L, the concentration of the sodium chloride is 220g/L-270g/L, and the concentration of the calcium chloride is 220g/L-270 g/L. In the high-pressure oxygen leaching step, the mass of the soaking solution is 12 to 16 times that of the waste copper material particles, so as to ensure that the reaction is carried out efficiently. In this embodiment, the high-pressure oxygen leaching process is completed in the high-pressure reaction kettle, and the high-pressure reaction kettle continuously stirs the waste copper particles in the reaction process, so as to further improve the reaction efficiency. Specifically, the reaction temperature is 115 ℃ to 120 ℃, and the oxygen pressure is 0.6MPa to 0.8 MPa.
Step 106: a reduction reaction step: and (3) placing part of the waste copper material particles into the leaching solution for full reaction, and filtering out material residues to obtain the electrolyte.
Specifically, after a part of waste copper material particles are placed into the leaching solution to react fully, material residues are filtered to obtain the electrolyte. In the reduction reaction step, the mass of the soaking solution is 12 to 16 times of the mass of the waste copper material particles. And regulating the pH value of the leaching solution to 4.5-4.8 by using a pH regulator. And continuously stirring the waste copper particles to improve the reaction efficiency.
Step 107: a rotational flow electrolysis step: and carrying out cyclone electrolysis treatment on the obtained electrolyte to obtain cathode copper.
Specifically, a rotational flow electrolysis system device is adopted to perform rotational flow electrolysis treatment on the obtained electrolyte to obtain the cathode copper tube. This is not described in detail in the prior art.
Above-mentioned copper smelting technology is handled to copper scrap material hyperbaric oxygen soaks, specifically, in proper order with the dust impurity on the copper scrap material wash, wash the greasy dirt on the copper scrap material, polish stubborn oxide and impurity on the copper scrap material off, get rid of the oxidation film on the copper scrap material. And crushing the waste copper material into particles so as to fully convert the copper simple substance into 2-valent copper ions. It is emphasized that in the present process, the leachate containing copper ions of value 2 is not directly subjected to electrolysis, but rather, a portion of the copper scrap particles is used to convert the copper ions of value 2 in the leachate to copper ions of value 1. And then carrying out electrolytic treatment on the electrolyte containing 1-valent copper ions to obtain cathode copper. By adopting the mode, on one hand, more waste copper particles can be treated, the production cost is reduced, the production efficiency is improved, on the other hand, the efficiency of electrolyzing the electrolyte containing 1-valent copper ions is higher, and the production efficiency is further improved. The copper smelting process for the high-pressure oxygen soaking treatment of the waste copper materials has low cost and high efficiency, and can meet the production requirements.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the 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 protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The copper smelting process for the high-pressure oxygen soaking treatment of the waste copper material is characterized by comprising the following steps of:
oil stain removal: cleaning the surface of the waste copper material with clear water, drying, and soaking the waste copper material in deoiling liquid for cleaning and deoiling after drying;
surface cleaning: cleaning the surface of the deoiled waste copper material with clear water, polishing, cleaning with clear water after polishing, and drying after cleaning;
removing the oxide film: soaking the dried waste copper material in a pickling solution to remove an oxide film on the surface;
crushing the waste copper material: crushing the waste copper material into particles;
a high-pressure oxygen leaching step: placing part of the waste copper material particles into a soaking solution, pressurizing and introducing oxygen, and filtering material residues to obtain a leaching solution after full reaction;
a reduction reaction step: placing part of the waste copper material particles into the leaching solution for full reaction, and filtering material residues to obtain electrolyte;
and (3) cyclone electrolysis: and carrying out cyclone electrolysis treatment on the obtained electrolyte to obtain cathode copper.
2. The process according to claim 1, wherein during the high pressure oxygen leaching step, the scrap copper particles are continuously stirred.
3. The process as claimed in claim 1, wherein in the high pressure oxygen leaching step, the high pressure oxygen leaching process is completed in a high pressure reaction vessel.
4. The process of claim 1, wherein during the reduction step, the scrap copper particles are continuously stirred.
5. The process of claim 1, wherein the soaking solution contains copper chloride, sodium chloride and calcium chloride, the concentration of the copper chloride is 54g/L-110g/L, the concentration of the sodium chloride is 220g/L-270g/L, and the concentration of the calcium chloride is 220g/L-270 g/L.
6. The process according to claim 1, wherein in the reduction step, the PH of the leachate is adjusted to 4.5 to 4.8 using a PH adjuster.
7. The process according to claim 1, wherein in the high pressure oxygen leaching step, the mass of the soaking liquid is 12 to 16 times the mass of a part of the waste copper material particles.
8. The process according to claim 1, wherein in the high pressure oxygen leaching step, the reaction temperature is 115 to 120 degrees celsius.
9. The process according to claim 1, wherein in the high pressure oxygen leaching step, the oxygen pressure is 0.6 to 0.8 MPa.
10. The process according to claim 1, wherein in the reduction reaction step, the mass of the soaking solution is 12 to 16 times the mass of a part of the waste copper material particles.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210497509.6A CN114717413A (en) | 2022-05-09 | 2022-05-09 | Copper smelting process for soaking waste copper material by high-pressure oxygen |
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| CN202210497509.6A CN114717413A (en) | 2022-05-09 | 2022-05-09 | Copper smelting process for soaking waste copper material by high-pressure oxygen |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3692647A (en) * | 1971-01-25 | 1972-09-19 | Wayne L Chambers | Electrolytic copper producing process |
| CN1688728A (en) * | 2002-10-15 | 2005-10-26 | 奥托库姆普联合股份公司 | Method for the recovery of metals using chloride leaching and extraction |
| CN102534656A (en) * | 2012-02-10 | 2012-07-04 | 嘉兴科菲冶金科技股份有限公司 | Process for recycling copper through electrodeposition by treating scrap copper materials by adopting cyclone electrolysis technology |
| CN104831064A (en) * | 2015-05-17 | 2015-08-12 | 李家元 | Process of efficiently recovering copper from lead matte according to oxygen pressure acid leaching and vortex electrolysis techniques |
-
2022
- 2022-05-09 CN CN202210497509.6A patent/CN114717413A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3692647A (en) * | 1971-01-25 | 1972-09-19 | Wayne L Chambers | Electrolytic copper producing process |
| CN1688728A (en) * | 2002-10-15 | 2005-10-26 | 奥托库姆普联合股份公司 | Method for the recovery of metals using chloride leaching and extraction |
| CN102534656A (en) * | 2012-02-10 | 2012-07-04 | 嘉兴科菲冶金科技股份有限公司 | Process for recycling copper through electrodeposition by treating scrap copper materials by adopting cyclone electrolysis technology |
| CN104831064A (en) * | 2015-05-17 | 2015-08-12 | 李家元 | Process of efficiently recovering copper from lead matte according to oxygen pressure acid leaching and vortex electrolysis techniques |
Non-Patent Citations (1)
| Title |
|---|
| 黄礼煌: "废弃机电电子电器资源化利用技术", 科学技术文献出版社, pages: 330 - 206 * |
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