Method for separating and recycling nickel in nickel-containing metal copper resource
By adding iron-containing refining agent and blown oxygen smelting during the ignition smelting process of nickel metal copper resources, combined with magnetic separation technology, the difficulty of copper-nickel fire separation and nickel recycling problems are solved, and efficient recycling of nickel and iron is achieved.
Patent Information
- Application Number
- CN202510078159.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-17
- Publication Date
- 2025-05-06
AI Technical Summary
In the prior art, when dealing with nickel-containing metal copper resources, it is difficult to separate copper-nickel fire, which makes it difficult to recycle nickel, and it is difficult to separate and extract nickel in smelting slag.
By heating the nickel-containing metal copper resources, adding iron-containing refining agent, controlling the smelting temperature and time, blowing oxygen to remove the smelting slag, and grinding the sludge for magnetic separation, and using the magnetic separation of nickel-iron spinel.
The efficient separation and recycling of nickel in nickel-containing metal copper resources is achieved, while improving the recovery rate of iron. The obtained magnetic products can be used for the production of nickel-ferroalloys.
Smart Images
Figure CN119932333A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of comprehensive utilization of multi-metal resources, and specifically discloses a method for separating and recycling nickel from nickel-containing copper resources. Background Art
[0002] my country's copper and nickel resources are relatively scarce. The reserves of copper and nickel resources account for only 4.1% and 1.6% of the world's total, respectively. The degree of external dependence has long exceeded 70% and 80%, respectively. Therefore, improving the utilization of copper and nickel resources, especially the recycling of secondary metal resources, is of great significance to the stable and sustainable development of my country's copper and nickel industries.
[0003] Scrap copper often contains a certain amount of nickel, especially when the scrap copper contains a lot of copper-nickel alloy waste, nickel-plated copper materials, and nickel-containing copper rice. For example, the addition of nickel can improve the conductivity, corrosion resistance, strength and toughness of white copper, and the nickel content in white copper is usually between 5% and 30%; nickel plating can improve the wear resistance, corrosion resistance and aesthetics of copper materials, and the nickel content in nickel-plated copper materials is usually between 2% and 30%. In addition, since copper ore often contains a certain amount of nickel, the crude copper obtained by smelting generally also contains a certain amount of nickel, especially the crude copper obtained by smelting copper-nickel sulfide ore, the nickel content can reach 1% to 5%. The efficient separation of copper and nickel and the value-added recycling of valuable metals in the separation products are key issues in the utilization of such nickel-containing copper resources.
[0004] At present, the processing technologies for this type of nickel-containing copper resources mainly include pyrometallurgy and wet leaching. For wet leaching, copper, nickel and impurities are usually dissolved at the same time when acid leaching is used, and the leaching is non-selective, requiring the addition of a complex impurity removal process; when ammonia leaching is used, copper and nickel are also dissolved at the same time, and copper and nickel are easily co-extracted by the extractant in the ammonia leaching system, making it difficult to separate copper and nickel. Pyrometallurgy has the advantages of high production efficiency and simple process, but there are also two outstanding problems: 1) Pyrometallurgy is difficult to separate copper and nickel. Under the action of traditional refining agents, the removal effect of nickel in copper liquid is not good. On the one hand, the residual nickel will affect the performance of copper materials, and on the other hand, it will reduce the recovery rate of nickel resources; 2) The nickel content in the smelting slag is low and the distribution is diffuse, which makes it very difficult to separate and extract nickel from the smelting slag. At present, in the production practice of using pyrometallurgy technology to treat such resources, the concentration dilution method is often used, that is, such resources are mixed into crude copper or high-quality scrap copper to reduce the nickel content in the copper liquid, so as to eliminate the influence of nickel on the performance of copper materials, and nickel is difficult to be recycled.
[0005] The present invention is proposed to solve the problems of copper-nickel separation and nickel recovery during pyrometallurgical smelting of nickel-containing copper resources. Summary of the invention
[0006] The invention discloses a method for separating and recycling nickel from nickel-containing copper resources. The method comprises the following steps: heating and melting the nickel-containing copper resources, adding a certain amount of iron-containing refining agent into the copper liquid, controlling the smelting temperature, blowing oxygen for smelting for a period of time, and then removing the smelting slag; grinding the cooled smelting slag to a certain fineness and then performing magnetic separation, and obtaining magnetic materials including nickel-iron spinel; the mass fraction of the iron-containing component in the iron-containing refining agent is greater than 60%, the valence state of the iron element is greater than or equal to 2, the molar ratio of Fe in the iron-containing refining agent to Ni in the copper resources is greater than or equal to 3, and the sum of the mass fractions of SiO2 and Al2O3 in the non-iron components is less than 30%.
[0007] Preferably, the mass fraction of the iron component in the iron-containing refining agent is greater than 70%, the valence of the iron element is greater than or equal to 2, and the sum of the mass fractions of SiO2 and Al2O3 in the non-iron components is less than 20%.
[0008] As a further preference, the mass fraction of the iron-containing component in the iron-containing refining agent is greater than 90%, the valence of the iron element is greater than or equal to 2, and the sum of the mass fractions of SiO2 and Al2O3 in the non-iron component is less than 8%. This solution can achieve simultaneous high-efficiency and high-density recovery of Fe and Ni while using a small amount of iron-containing refining agent.
[0009] The present invention discloses a method for separating and recycling nickel from nickel-containing copper resources. The nickel-containing copper resources include one or more of nickel-containing scrap copper and nickel-containing crude copper.
[0010] The present invention discloses a method for separating and recycling nickel from nickel-containing copper resources, wherein the mass fraction of copper in the nickel-containing copper resources is greater than 70%. The nickel content is not limited, but in practical application, the mass percentage of nickel in the nickel-containing copper resources can be controlled to be 0.1% to 10%. In industrial application, when Ni is less than 0.1%, the economic value of recycling is low.
[0011] The invention discloses a method for separating and recycling nickel from nickel-containing copper resources. The amount of the iron-containing refining agent is 1% to 60% of the mass ratio of the scrap copper.
[0012] Preferably, when the mass fraction of the iron-containing component in the iron-containing refining agent is greater than 90%, the molar ratio of the iron-containing refining agent to the scrap copper is 3 to 15, more preferably 3 to 10, which of course includes 3 to 6, 3.5 to 8, etc. At this time, a small amount of iron-containing refining agent can achieve simultaneous high-efficiency and high-density recovery of Fe and Ni. Moreover, this solution is particularly suitable for raw materials with a nickel content of 1 to 10%.
[0013] The invention discloses a method for separating and recycling nickel from nickel-containing copper resources. The smelting temperature of the nickel-containing copper resources is 1100-1300° C., preferably 1150-1250° C., and the smelting time is 30-180 min.
[0014] The invention discloses a method for separating and recycling nickel from nickel-containing copper resources. The smelting slag is ground to a particle size of less than 0.074 mm, and the mass percentage thereof is not less than 80%. Then, weak magnetic separation is performed. The magnetic field strength of the weak magnetic separation is 800 to 1800 Oe. The main components of the obtained magnetic material are nickel-iron spinel and magnetite.
[0015] A method for separating and recycling nickel from nickel-containing copper resources using the above technical solution is briefly described as follows: During the oxygen blowing smelting process of nickel-containing copper resources, metallic nickel can be oxidized to NiO, but NiO is distributed between copper liquid and slag, making it difficult to separate and purify. The iron-containing component in the iron-containing refining agent is Fe2O3 or is easily converted into Fe2O3 under oxygen blowing smelting conditions. NiO is easy to combine with Fe2O3 to form nickel-iron spinel NiO·Fe2O3 and enter the smelting slag. After the smelting is completed, the nickel in the nickel-containing copper resources can be separated by slagging. Nickel-iron spinel has strong magnetism. The smelting slag is finely ground and then magnetically separated to achieve the separation of nickel-iron spinel from other components.
[0016] 4Fe3O4+O2(g)=6Fe2O3
[0017] Fe2O3·nH2O=Fe2O3+nH2O(g)
[0018] 4FeCO3+O2(g)=2Fe2O3+4CO2(g)
[0019] NiO+Fe2O3=NiO·Fe2O3(NiFe2O4)
[0020] The advantages of the present invention are:
[0021] 1) Fire smelting technology is used to separate nickel from nickel-containing copper resources. Fire smelting refining agents are cheap and easy to obtain, green and environmentally friendly, and are extremely convenient for industrial promotion and application;
[0022] 2) The present invention is ingeniously designed, and utilizes an iron-containing refining agent to convert nickel in copper liquid into nickel-iron spinel, thereby achieving efficient separation of copper and nickel and providing conditions for efficient enrichment and recycling of nickel components;
[0023] 3) The present invention can not only separate and recycle nickel, but also recycle the valuable metal iron in the refining agent, which is difficult to achieve with the existing methods. The obtained magnetic product containing nickel and iron can be used as raw material for the production of nickel-iron alloy / stainless steel. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 Flow chart of the process designed for the present invention. DETAILED DESCRIPTION
[0025] The present invention will be further described below in conjunction with the embodiments.
[0026] Embodiment 1:
[0027] The mass fraction of copper in a nickel-containing scrap copper is 98.6%, the mass fraction of nickel is 0.1%, the mass fraction of the iron component in a certain iron-containing refining agent is 71%, the mass fractions of non-iron components SiO2 and Al2O3 are 10% and 6% respectively, and the remainder is other impurities (such as CaO, MgO, S, burnout, etc.). After melting the nickel-containing scrap copper, add an iron-containing refining agent accounting for 4.0% of the mass ratio of the nickel-containing scrap copper (the molar ratio of Fe in the iron-containing refining agent to Ni in the metallic copper resource is Fe:Ni=20.9), and carry out oxygen blowing smelting, maintain the smelting temperature at 1200℃, and the smelting time is 60min. After the smelting is completed, the slag is removed. The cooled smelting slag is ground to a particle size of -0.074 mm accounting for 90.0wt.% and then subjected to weak magnetic separation. The magnetic field strength of the weak magnetic separation is 1200Oe. The main components of the obtained magnetic material are nickel-iron spinel and magnetite, with a Ni content of 1.8% and a Fe content of 37.9%. It can be used as a high-quality raw material for preparing nickel-iron alloy. The Ni recovery rate of the whole smelting-magnetic separation process is 71.2%, and the Fe recovery rate is 75.4%.
[0028] Embodiment 2:
[0029] The mass fraction of copper in a nickel-containing scrap copper is 87.2%, the mass fraction of nickel is 10.0%, the mass fraction of the iron component in a certain iron-containing refining agent is 95%, the mass fraction of the non-iron component SiO2 is 2%, and the remainder is other impurities (such as CaO, MgO, S, burnout, etc.). After melting the nickel-containing scrap copper, add an iron-containing refining agent (the molar ratio of Fe in the iron-containing refining agent to Ni in the metallic copper resource is Fe:Ni=3.50) accounting for 50.0% of the mass ratio of the nickel-containing scrap copper, and carry out oxygen blowing smelting, maintain the smelting temperature at 1200°C, the smelting time is 90min, and slag is removed after the smelting is completed. The cooled smelting slag is ground to a particle size of -0.074 mm accounting for 90.0wt.% and then subjected to weak magnetic separation. The magnetic field strength of the weak magnetic separation is 1200Oe. The main component of the obtained magnetic material is nickel-iron spinel, with a Ni content of 15.1% and a Fe content of 43.8%. It can be used as a high-quality raw material for preparing nickel-iron alloy. The Ni recovery rate of the whole smelting-magnetic separation process is 90.3%, and the Fe recovery rate is 78.8%.
[0030] Embodiment 3:
[0031] The mass fraction of copper in a nickel-containing crude copper is 94.5%, the mass fraction of nickel is 3.8%, the mass fraction of the iron component in a certain iron-containing refining agent is 95%, the mass fraction of the non-iron component SiO2 is 2%, and the remainder is other impurities (such as CaO, MgO, S, burnout, etc.). After melting the nickel-containing scrap copper, add an iron-containing refining agent (the molar ratio of Fe in the iron-containing refining agent to Ni in the metallic copper resource is Fe:Ni=5.53) accounting for 30% of the mass ratio of the nickel-containing scrap copper, and carry out oxygen blowing smelting, maintain the smelting temperature at 1200℃, the smelting time is 90min, and slag is removed after the smelting is completed. The cooled smelting slag is ground to a particle size of -0.074 mm accounting for 90.0wt.% and then subjected to weak magnetic separation. The magnetic field strength of the weak magnetic separation is 1200Oe. The main components of the obtained magnetic material are nickel-iron spinel and magnetite, with a Ni content of 8.2% and a Fe content of 38.6%. It can be used as a high-quality raw material for preparing nickel-iron alloy. The Ni recovery rate of the whole smelting-magnetic separation process is 91.4%, and the Fe recovery rate is 81.9%.
[0032] Embodiment 4:
[0033] The mass fraction of copper in a nickel-containing crude copper is 94.5%, the mass fraction of nickel is 3.8% (i.e., a nickel-containing crude copper is the same batch as Example 3), the mass fraction of the iron-containing component of a certain iron-containing refining agent is 71%, and the mass fractions of non-iron components SiO2 and Al2O3 are 10% and 6% respectively, and the remainder is other impurities (such as CaO, MgO, S, burnout, etc.). After melting the nickel-containing scrap copper, add an iron-containing refining agent (the molar ratio of Fe in the iron-containing refining agent to Ni in the metallic copper resource is Fe:Ni=5.51) accounting for 40% of the mass ratio of the nickel-containing scrap copper, carry out oxygen blowing smelting, keep the smelting temperature at 1200°C, the smelting time is 90min, and slag is skimmed after the smelting ends. The smelting slag after cooling is ground to -0.074mm particle size accounting for 90.0wt.% and then weak magnetic separation is carried out, the magnetic field intensity of the weak magnetic separation is 1200Oe, the main component of the obtained magnetic material is nickel-iron spinel and magnetite, Ni content is 7.8%, Fe content is 35.4%, which can be used as the high-quality raw material for preparing nickel-iron alloy, and the Ni recovery rate of the whole process of smelting-magnetic separation is 90.8%, and the Fe recovery rate is 78.8%. In the present embodiment, although the use of iron-containing refining agent is increased, the recovery rates of Ni and Fe both have a certain degree of decline (compared to Example 3).
[0034] Embodiment 5:
[0035] The mass fraction of copper in a nickel-containing crude copper is 97.6%, the mass fraction of nickel is 1.1%, the mass fraction of the iron component in a certain iron-containing refining agent is 95%, the mass fraction of the non-iron component SiO2 is 2%, and the remainder is other impurities (such as CaO, MgO, S, burnout, etc.). After melting the nickel-containing scrap copper, add an iron-containing refining agent (the molar ratio of Fe in the iron-containing refining agent to Ni in the metallic copper resource is Fe:Ni=6.37) accounting for 10% of the mass ratio of the nickel-containing scrap copper, and carry out oxygen blowing smelting, maintain the smelting temperature at 1200℃, the smelting time is 90min, and slag is removed after the smelting is completed. The cooled smelting slag is ground to a particle size of -0.074 mm accounting for 90.0wt.% and then subjected to weak magnetic separation. The magnetic field strength of the weak magnetic separation is 1200Oe. The main components of the obtained magnetic material are nickel-iron spinel and magnetite, with a Ni content of 7.6% and a Fe content of 41.0%. It can be used as a high-quality raw material for preparing nickel-iron alloy. The Ni recovery rate of the whole smelting-magnetic separation process is 91.5%, and the Fe recovery rate is 81.6%.
[0036] Embodiment 6:
[0037] The mass fraction of copper in a nickel-containing crude copper is 97.6%, the mass fraction of nickel is 1.1% (i.e., a nickel-containing crude copper and embodiment 5 are the same batch of materials), the mass fraction of the iron-containing component of a certain iron-containing refining agent is 71%, and the mass fractions of non-iron components SiO2 and Al2O3 are 10% and 6% respectively, and the remainder is other impurities (such as CaO, MgO, S, burnout, etc.). After melting the nickel-containing scrap copper, an iron-containing refining agent (the molar ratio of Fe in the iron-containing refining agent to Ni in the metallic copper resource is Fe:Ni=7.14) accounting for 15% of the mass ratio of the nickel-containing scrap copper is added, oxygen blowing smelting is carried out, the smelting temperature is kept at 1200°C, the smelting time is 90min, and slag is skimmed after the smelting is completed. The smelting slag after cooling is ground to -0.074mm particle size accounting for 90.0wt.% and then weak magnetic separation is carried out, the magnetic field intensity of the weak magnetic separation is 1200Oe, the main component of the obtained magnetic material is nickel-iron spinel and magnetite, Ni content is 7.2%, Fe content is 41.7%, which can be used as the high-quality raw material for preparing nickel-iron alloy, and the Ni recovery rate of the whole process of smelting-magnetic separation is 90.6%, and the Fe recovery rate is 77.4%. In the present embodiment, although the use of iron-containing refining agent is increased, the recovery rates of Ni and Fe both have a certain degree of decline (compared to Example 5).
[0038] Comparative Example 1:
[0039] The mass fraction of copper in a nickel-containing crude copper is 94.5%, the mass fraction of nickel is 3.8%, the mass fraction of the iron component in a certain iron-containing refining agent is 28%, the mass fractions of non-iron components SiO2 and Al2O3 are 35% and 10% respectively, and the remainder is other impurities (such as CaO, MgO, S, burnout, etc.). After melting the nickel-containing scrap copper, add an iron-containing refining agent (the molar ratio of Fe in the iron-containing refining agent to Ni in the metallic copper resource is Fe:Ni=1.36) accounting for 25% of the mass ratio of the nickel-containing scrap copper, and carry out oxygen blowing smelting, maintain the smelting temperature at 1200℃, and the smelting time is 90min. After the smelting is completed, the slag is removed. The cooled smelting slag was ground to a particle size of -0.074 mm accounting for 90.0wt.% and then subjected to weak magnetic separation. The magnetic field strength of the weak magnetic separation was 1200Oe. The main components of the obtained magnetic material were nickel-iron spinel and magnetite, with a Ni content of 6.4% and a Fe content of 11.78%. The Ni recovery rate of the entire smelting-magnetic separation process was only 24.8%, and the Fe recovery rate was 35.4%, which was significantly lower than that in Example 4.
Claims
1. A method for separating and recycling nickel from nickel-containing copper resources, characterized in that: The nickel-containing copper resource is heated and melted, a certain amount of iron-containing refining agent is added to the copper liquid, the smelting temperature is controlled, and oxygen is blown for smelting for a period of time, and then the smelting slag is removed; the cooled smelting slag is ground to a certain fineness and then magnetically separated, and the obtained magnetic material includes nickel-iron spinel; the mass fraction of the iron component in the iron-containing refining agent is greater than 60%, the valence state of the iron element is greater than or equal to 2, the molar ratio of Fe in the iron-containing refining agent to Ni in the copper resource is greater than or equal to 3, and the sum of the mass fractions of SiO2 and Al2O3 in the non-iron components is less than 30%.
2. The method for separating and recycling nickel from nickel-containing copper resources according to claim 1, characterized in that: The mass fraction of the iron component in the iron-containing refining agent is greater than 70%, the valence of the iron element is greater than or equal to 2, and the sum of the mass fractions of SiO2 and Al2O3 in the non-iron component is less than 20%.
3. The method for separating and recycling nickel from nickel-containing copper resources according to claim 1, characterized in that: The mass fraction of the iron component in the iron-containing refining agent is greater than 90%, the valence of the iron element is greater than or equal to 2, and the sum of the mass fractions of SiO2 and Al2O3 in the non-iron component is less than 8%.
4. The method for separating and recycling nickel from nickel-containing copper resources according to claim 1, characterized in that: The nickel-containing metallic copper resources include one or more of nickel-containing scrap copper and nickel-containing crude copper.
5. The method for separating and recycling nickel from nickel-containing copper resources according to claim 1, characterized in that: The mass fraction of copper in the nickel-containing copper resource is greater than 70%.
6. The method for separating and recycling nickel from nickel-containing copper resources according to claim 1, characterized in that: The amount of the iron-containing refining agent is 1% to 60% of the mass ratio of the scrap copper.
7. The method for separating and recycling nickel from nickel-containing copper resources according to claim 1, characterized in that: When the mass fraction of the iron-containing component in the iron-containing refining agent is greater than 90%, the molar ratio of the iron-containing refining agent to the scrap copper is 3 to 15.
8. The method for separating and recycling nickel from nickel-containing copper resources according to claim 1, characterized in that: The smelting temperature of the nickel-containing copper resource is 1100-1300° C., preferably 1150-1250° C., and the smelting time is 30-180 min.
9. The method for separating and recycling nickel from nickel-containing copper resources according to claim 1, characterized in that: The smelting slag is ground to a particle size of less than 0.074 mm with a mass percentage of not less than 80% and then subjected to weak magnetic separation. The magnetic field strength of the weak magnetic separation is 800-1800 Oe. The main components of the obtained magnetic material are nickel-iron spinel and magnetite.