CN117512354A - Method for reducing copper content in slag by smelting reclaimed copper - Google Patents
Method for reducing copper content in slag by smelting reclaimed copper Download PDFInfo
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- CN117512354A CN117512354A CN202311458664.8A CN202311458664A CN117512354A CN 117512354 A CN117512354 A CN 117512354A CN 202311458664 A CN202311458664 A CN 202311458664A CN 117512354 A CN117512354 A CN 117512354A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000010949 copper Substances 0.000 title claims abstract description 149
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 148
- 239000002893 slag Substances 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000003723 Smelting Methods 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 9
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 9
- 229940112669 cuprous oxide Drugs 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000006004 Quartz sand Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000010309 melting process Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/003—Bath smelting or converting
- C22B15/0036—Bath smelting or converting in reverberatory furnaces
-
- 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
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
-
- 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
- C22B7/001—Dry processes
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of metallurgy, and provides a method for reducing copper content in slag by smelting reclaimed copper.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for reducing copper content in slag by smelting reclaimed copper.
Background
Copper production can be achieved in two ways: firstly, copper ores are mined from nature, and the other is by recycling secondary copper resources. The traditional copper smelting mainly uses copper ores as raw materials, and most of copper ores exist in the form of sulfides, wherein sulfur contains higher heat. Thus, copper ore is fed into a pyrometallurgical furnace and slag formers are added in a high temperature environment to produce a mixture based on copper, iron and sulfur, i.e. copper sulfur. The copper and sulfur are then fed into a converter for oxidation converting, a slag former is added in a high temperature environment, and iron and sulfur are removed to obtain blister copper. Typically, blister copper has a copper content in excess of 98%. The blister copper is fed to a fire refining furnace where small amounts of impurities are further removed by oxidation-reduction to yield an anode plate having a copper content in excess of 99%. And (3) electrolyzing the anode plate to finally obtain electrolytic refined copper as a final product.
At present, a reverberatory furnace is used for smelting copper, the copper content of slag is generally 20% or more, and the copper loss is large. The grade of the regenerated copper is generally higher, and the smelting of the regenerated copper with higher grade (Cu is more than or equal to 95 percent) is easy to lead to further improvement of copper content in slag once the process is not controlled in place.
CN201110089504.1 discloses a method for depletion of copper refining slag, comprising the steps of: adding the recovered waste copper into a reverberatory furnace, heating and melting, inserting a blast pipe into the copper melt, blowing air, stirring and oxidizing while blowing air to oxidize impurities and part of copper into cuprous oxide; when the section of the copper liquid is brick red, quartz sand is added according to 1.2% -1.4% of the total weight of the charged materials for slagging, so that oxidized impurities such as Fe, pb, sn and the like in the copper liquid and quartz generate silicate slag; covering the slag with carbonaceous reducing agent in the amount of 0.13-0.17% of the total amount of waste copper, inserting blast pipe into copper melt, blowing air, stirring for 5-10 min, and reducing copper into copper liquid phase after some copper has entered slag phase. The copper content in the slag is reduced by about 35 percent, which is favorable for recycling the regenerated copper resource. According to the method, after the slag former is added, a carbonaceous reducing agent is added to cover the slag, and then air is blown in for stirring, so that copper which has entered into the slag phase is reduced and enters the copper liquid phase again, and further copper in the slag is reduced.
However, after the copper in the slag phase is reduced, the slag skimming process is not disclosed, and in actual work, copper liquid needs to be continuously stirred in the slag skimming process, so that the copper liquid is easy to splash and float on the surface of a slag layer to be less than sedimentation reduction, and the slag skimming process is one of the main factors causing higher copper content in the slag; in addition, in the technical process of the patent, how to control the oxidation process is not disclosed, but uneven oxidation and too deep oxidation can lead to insufficient oxidation of copper materials, so that slag copper is not separated in place, and the copper is another main factor leading to higher copper content of slag.
Based on the above, the technical problems solved by the scheme are as follows: how to further improve the slag type and reduce the copper content of the slag.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for reducing copper content in slag by smelting reclaimed copper, which not only can reduce the mechanical loss of copper in the slag skimming process, but also can reduce the chemical loss of copper in the oxidizing and slag forming process, thereby greatly reducing copper content in the slag.
The technical scheme of the invention is as follows:
a method for smelting reclaimed copper to reduce copper content in slag, which comprises the following steps,
step 1, detecting the iron content of a reclaimed copper material;
step 2, putting the copper material into a reverberatory furnace to be melted into copper liquid, and introducing a gas medium with the pressure of 0.4-0.5 MPa to continuously stir the copper liquid in the melting process, wherein the temperature is controlled at 1085-1100 ℃;
step 3, introducing normal oxygen wind with the pressure of 0.4-0.5 MPa into the copper liquid to oxidize the copper liquid, and continuously changing the action position of the normal oxygen wind in the process, wherein the temperature is controlled at 1085-1150 ℃;
step 4, adding the slag former into a reverberatory furnace according to the calculated iron content measured in the step 1, and then carrying out shallow reduction on copper liquid to reduce cuprous oxide into copper simple substance and reduce high-valence oxidative impurities into low-valence oxidative impurities;
step 5, removing slag, inserting a blast pipe, enabling an air port of the blast pipe to be close to the surface of the copper liquid, and then introducing normal oxygen wind or inert gas with the pressure of 0.4-0.5 MPa into the blast pipe to blow the slag on the surface of the copper liquid to the periphery of a slag port;
and 6, skimming, namely manually skimming slag around the slag hole until the thickness of the slag layer is less than 1cm, and controlling the temperature at 1140-1170 ℃.
In the method for smelting the regenerated copper to reduce the copper content in the slag, the gas medium in the step 2 is subjected to normal oxygen wind or inert gas.
In the method for smelting the reclaimed copper to reduce the copper content in the slag, the slag former is quartz sand; in the step 4, according to FeO: and (3) carrying out quartz sand slag former proportioning by SiO2=2:1.
In the above method for smelting the reclaimed copper to reduce the copper content in the slag, in the step 5, when no copper liquid splashes to the slag layer in the slag removing process, the step 6 is directly carried out; and (3) when the copper liquid splashes to the slag layer in the slag removing process, standing the slag layer for more than 10 minutes, and then entering the step (6).
In the above method for smelting the reclaimed copper to reduce the copper content in the slag, in the step 6, the slag is removed by adopting a wooden slag removing or an iron slag removing.
In the method for smelting the regenerated copper to reduce the copper content in the slag, the temperature in the step 2 is controlled at 1085-1090 ℃; the temperature of the step 3 is controlled to be 1085-1100 ℃; the temperature of the step 6 is controlled between 1140 ℃ and 1160 ℃.
One of the above technical solutions of the present invention has at least one of the following advantages or beneficial effects:
the slag removing process is optimized, and the blast pipe is inserted into the blast pipe and the tuyere of the blast pipe is close to the surface of the copper liquid, so that the method has the advantages that excessive oxygen is not brought into the copper liquid, and copper metal splashes are prevented or reduced from entering a slag layer and being brought into a slag phase along with a slag removing process, so that the mechanical loss of copper in the slag removing process is reduced; meanwhile, by improving the operation method of the traditional oxidation slagging process, particularly, the normal oxygen wind is continuously changed in position and kept at low temperature for oxidation, so that the problems of uneven oxidation and over-deep oxidation of copper materials are avoided, the generation of cuprous oxide between copper slag is reduced, the slag is further improved, and the chemical loss of copper in the oxidation slagging process is reduced.
Drawings
Fig. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for smelting reclaimed copper to reduce copper content in slag, which comprises the following steps,
step 1, detecting the iron content of a reclaimed copper material;
step 2, putting the copper material into a reverberatory furnace to be melted into copper liquid, and introducing normal oxygen wind with the pressure of 0.5MPa to continuously stir the copper liquid in the melting process, wherein the temperature is controlled at 1085-1100 ℃;
step 3, introducing normal oxygen wind with the pressure of 0.5MPa into the copper liquid to oxidize the copper liquid, and continuously changing the action position of the normal oxygen wind in the process, wherein the temperature is controlled at 1085-1150 ℃;
and 4, taking the iron content measured in the step 1 as a calculation basis and according to FeO: adding quartz sand with the ratio of SiO2=2:1 into a reverberatory furnace, then carrying out shallow reduction on copper liquid, reducing cuprous oxide into copper simple substance, and reducing high-valence oxidative impurities into low-valence oxidative impurities;
step 5, removing slag, inserting a blast pipe, enabling an air port of the blast pipe to be close to the surface of the copper liquid, and then introducing normal oxygen wind with the pressure of 0.5MPa into the blast pipe to blow the slag on the surface of the copper liquid to the periphery of the slag port; in the step 5, when no copper liquid splashes to a slag layer in the slag removing process, directly entering the step 6; and (3) when the copper liquid splashes to the slag layer in the slag removing process, standing the slag layer for 30 minutes, and then entering the step (6).
And 6, skimming, namely skimming the slag around the slag hole manually by adopting wood slag until the thickness of the slag layer is less than 1cm, and controlling the temperature to be 1140-1170 ℃.
Example 2
Substantially the same as in example 1, except that the temperature in the step 2 is controlled to 1085 ℃ to 1090 ℃; the temperature of the step 3 is controlled to be 1085-1100 ℃; the temperature of the step 6 is controlled between 1140 ℃ and 1160 ℃.
Example 3
Substantially the same as in example 1, except that in the above-mentioned step 5, when the copper liquid splashes to the slag layer during the slag removal, the slag layer is left for 10 minutes, and then the process proceeds to step 6.
Comparative example 1
Substantially the same as in example 1, except that the temperature in the step 2 is controlled to be 1200 ℃ to 1260 ℃; the temperature in the step 3 is controlled to 1250-1300 ℃; the temperature in the step 6 is controlled between 1250 ℃ and 1300 ℃.
Comparative example 2
Substantially the same as in example 1, except that in the above-mentioned step 5, when the copper liquid splashes to the slag layer during the slag removal, the slag layer is left for 5 minutes, and then the process proceeds to step 6.
Comparative example 3
Substantially the same as in example 1, except that in step 5, when the copper liquid splashes to the slag layer during the slag removal process, the slag layer is not left to stand, and the process proceeds directly to step 6.
Comparative example 4
Substantially the same as in example 1, except that the action position of the normal oxygen wind during the step 3 was maintained at the center of the reverberatory furnace.
Performance test: 300 tons of copper materials in the same batch are selected for refining respectively.
Table 1: composition of slag component of each mode
| Project | Total mass kg of slag | Mass kg of copper in slag | Slag copper% |
| Example 1 | 17550 | 2608 | 14.86 |
| Example 2 | 16225 | 2193 | 13.52 |
| Example 3 | 17963 | 2806 | 15.62 |
| Comparative example 1 | 20332 | 4544 | 22.35 |
| Comparative example 2 | 18025 | 2905 | 16.12 |
| Comparative example 3 | 18372 | 3382 | 18.41 |
| Comparative example 4 | 20662 | 4860 | 23.52 |
Analysis of results:
the reason for the lower copper content of the slag of example 2 compared to example 1 and example 2 is that the oxidation at lower temperature results in lower oxygen content in the copper bath, less high melting point cuprous oxide is produced, more clear separation of slag copper and less copper in the slag skimming.
The slag of example 3 is more copper-containing than example 1 and example 3, because the slag layer requires sufficient settling time to ensure better slag copper clarification. When the slag layer is left standing for a short time, a small amount of copper particles cannot be effectively carried into the slag through the slag layer.
Comparative example 1 and comparative example 1, the slag of comparative example 1 contains more copper because the oxygen content in the copper liquid is excessively high due to oxidation at high temperature, and a large amount of high melting point cuprous oxide is generated between the slag and the copper liquid, resulting in poor slag fluidity, difficult slag skimming, and a large amount of cuprous oxide is carried into the slag along with the slag skimming process.
Comparative examples 1, 3 and 2, the slag of comparative example 2 has the highest copper content because the slag layer of comparative example 2 has the shortest standing time and the copper slag has the worst clarifying effect.
The reason for the highest copper content in the slag of comparative examples 1, 2 and 3 is that the copper liquid splashed during slag removal is carried into the slag along with the slag removal process after the copper liquid is placed on the slag layer for clarification.
In comparative examples 1 and 4, the slag of comparative example 4 contains higher copper because the oxidation of comparative example 4 is not uniform enough and the oxidation of impurities is not uniform, and a large amount of impurity oxides cannot be effectively combined with the slag former to produce a low melting point material, resulting in high slag melting point and poor slag fluidity. And the operation of comparative example 4 is liable to cause an increase in oxidation time, thereby locally generating more high-melting-point cuprous oxide, further deteriorating slag type. The above factors result in a slag with higher copper content.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (6)
1. A method for smelting regenerated copper to reduce copper content in slag is characterized by comprising the following steps,
step 1, detecting the iron content of a reclaimed copper material;
step 2, putting the copper material into a reverberatory furnace to be melted into copper liquid, and introducing a gas medium with the pressure of 0.4-0.5 MPa to continuously stir the copper liquid in the melting process, wherein the temperature is controlled at 1085-1100 ℃;
step 3, introducing normal oxygen wind with the pressure of 0.4-0.5 MPa into the copper liquid to oxidize the copper liquid, and continuously changing the action position of the normal oxygen wind in the process, wherein the temperature is controlled at 1085-1150 ℃;
step 4, adding the slag former into a reverberatory furnace according to the calculated iron content measured in the step 1, and then carrying out shallow reduction on copper liquid to reduce cuprous oxide into copper simple substance and reduce high-valence oxidative impurities into low-valence oxidative impurities;
step 5, removing slag, inserting a blast pipe, enabling an air port of the blast pipe to be close to the surface of the copper liquid, and then introducing normal oxygen wind or inert gas with the pressure of 0.4-0.5 MPa into the blast pipe to blow the slag on the surface of the copper liquid to the periphery of a slag port;
and 6, skimming, namely manually skimming slag around the slag hole until the thickness of the slag layer is less than 1cm, and controlling the temperature at 1140-1170 ℃.
2. The method for smelting secondary copper reduction slag copper according to claim 1, wherein the gaseous medium in the step 2 is a normal oxygen wind or an inert gas.
3. The method for smelting reclaimed copper to reduce copper content in slag as claimed in claim 1, wherein the slag former is quartz sand; in the step 4, according to FeO: and (3) carrying out quartz sand slag former proportioning by SiO2=2:1.
4. The method for reducing copper content in slag in smelting regenerated copper according to claim 1, wherein in the step 5, when no copper liquid splashes to a slag layer in the slag removing process, the method directly enters the step 6; and (3) when the copper liquid splashes to the slag layer in the slag removing process, standing the slag layer for more than 10 minutes, and then entering the step (6).
5. The method for reducing copper content in slag for smelting secondary copper according to claim 4, wherein the step 6 is performed by adopting wooden slag raking or iron slag raking.
6. The method for smelting secondary copper to reduce copper content in slag according to claim 1, wherein the temperature in the step 2 is controlled to 1085 ℃ to 1090 ℃; the temperature of the step 3 is controlled to be 1085-1100 ℃; the temperature of the step 6 is controlled between 1140 ℃ and 1160 ℃.
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| CN215162900U (en) * | 2021-06-02 | 2021-12-14 | 镇江市坤洋冶金设备有限公司 | Gas control device for blowing and removing slag |
| CN113999996A (en) * | 2021-09-26 | 2022-02-01 | 江西铜业技术研究院有限公司 | Method for preparing anode plate by complex copper-containing material through fire refining |
| CN116516082A (en) * | 2023-05-31 | 2023-08-01 | 日照钢铁控股集团有限公司 | Low-cost and high-efficiency molten iron slag removing method |
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