CN-117512372-B - Method for deeply depleting copper-iron nonferrous metal solid waste and preparing copper-iron alloy

Abstract

The invention provides a method for deeply depleting copper-iron nonferrous metal solid waste and preparing copper-iron alloy, relates to the technical field of comprehensive recovery and utilization of nonferrous metal solid waste, and solves the technical problems that the existing copper slag pyrogenic depletion recovery technology is low in copper-iron recovery and utilization rate, and the recovered magnetic iron content is low and difficult to utilize. The invention uses carbon-containing waste as reducing agent and part of white mud as slag former, and simultaneously utilizes trace TiO 2 , na 2 O and the like in the white mud to strengthen the smelting process of copper slag. The recovery rate of copper and iron in the deep depletion process reaches more than 90%, the residual content of copper and iron in slag is respectively reduced to below 0.1wt% and below 4.0wt%, papermaking white mud and various carbon-containing wastes are adopted in the smelting process, the comprehensive utilization of solid wastes is realized, and the resource utilization efficiency is improved.

Inventors

• REN YONGZHUAN
• ZHOU QUNXIAN
• ZHOU SHIWEI
• TANG YURONG
• LI HONGMING
• XI JUN
• GAO RONG
• ZHANG YUYUN
• WANG CHANGHUI
• YANG ZHENGYU
• Yuan Binxiong
• LI JIANCHUN
• CHEN ENLIN
• LI FABIAO
• Wu Fawei
• WEI YONGGANG
• CHEN LEI
• LI BO
• Cui Yuxun
• QU GUORUI
• LU YONGJIE
• PENG WENFENG

Assignees

• 凉山矿业股份有限公司
• 昆明理工大学

Dates

Publication Date

20260505

Application Date

20231103

Claims (8)

1. 1. The method for deeply depleting copper-iron nonferrous metal solid waste and preparing copper-iron alloy is characterized by comprising the following steps: S1, drying, grinding and sieving copper slag and carbon-containing waste materials and papermaking white mud, and mixing; s2, placing the mixed material obtained in the step S1 into a smelting furnace, heating, introducing protective gas N 2 , and then preserving heat for a period of time; S3, separating the copper-iron metal melt obtained by smelting in the step S2 from slag, and discharging the slag from a slag outlet of the smelting furnace; s4, continuously refining and impurity-removing the residual copper-iron metal melt after slag removal in the step S3 in a smelting furnace, introducing protective gas N 2 , adding a desulfurizing agent, and controlling the sulfur content of impurities in the copper-iron metal melt to be less than 0.5wt%; S5, adding pure copper into the refined and impurity-removed copper-iron metal melt to continuously refine to obtain a copper-iron alloy product; In the step S1, the mass ratio of the copper slag to the carbon-containing waste to the papermaking white mud is 100:8-16:10-20, the temperature of the mixed material is raised to 1350-1450 ℃ in a smelting furnace, and the heat preservation time is 60-120 min.
2. 2. The method for deep depletion of copper-iron nonferrous metal solid waste and preparation of copper-iron alloy according to claim 1, wherein in the step S1, the papermaking white mud is derived from solid waste generated in the alkaline pulping process in the papermaking process, and the main components of the papermaking white mud are CaCO 3 with the concentration of >90 wt%, mgO with the concentration of 1.1wt% -1.2% by weight, siO 2 with the concentration of 1.1% -1.3% -wt% and Al 2 O 3 with the concentration of 2.4% -2.6% by weight.
3. 3. The method for deep depletion of copper-iron nonferrous metal solid waste and preparation of copper-iron alloy according to claim 2, wherein in the step S1, the papermaking white mud further contains 0.15-0.25 wt% of TiO 2 、0.45wt％～0.55wt％Na 2 O and other trace elements.
4. 4. A process for deep depletion of copper-iron nonferrous metal solid wastes and preparing copper-iron alloy according to any one of claims 1-3, wherein in said step S1, the fraction mass ratio of the carbon-containing wastes with particle size of <0.074mm is more than 90%.
5. 5. A process for the deep depletion of copper-iron nonferrous metals and for the preparation of copper-iron alloys according to any of claims 1 to 3 characterized in that in said step S1 the fraction of copper slag with particle size of <0.30mm is greater than 95% by mass.
6. 6. A process for the deep depletion of copper-iron nonferrous metals and for the preparation of copper-iron alloys according to any one of claims 1 to 3, characterized in that in said step S3 the copper-iron content of the reject slag is determined.
7. 7. The method for deep depletion of copper-iron nonferrous metal solid waste and preparation of copper-iron alloy according to claim 6, wherein the method is characterized in that according to the analysis result of the content of residual copper-iron in slag discharged in the step S3, the amount of pure copper added in the step S5 by continuous refining is determined, so that the copper-iron metal melt has a copper-iron mass ratio of 1:8-9.5.
8. 8. The method for deep depletion of nonferrous copper metal and copper-iron alloy according to claim 7, wherein the copper content of the discharged slag is less than 0.1 wt% and the iron content of the discharged slag is less than 4.0 wt% in step S3.

Description

Method for deeply depleting copper-iron nonferrous metal solid waste and preparing copper-iron alloy Technical Field The invention relates to the technical field of comprehensive recycling of nonferrous metal solid wastes, in particular to a method for deeply depleting copper-iron nonferrous metal solid wastes and preparing copper-iron alloy. Background Copper is an important nonferrous metal, has good electric conduction, heat conduction and corrosion resistance, and is widely applied to the fields of electronics, electricity, construction, chemical industry and the like. However, with the increasing consumption of copper, a great deal of copper slag is produced, which has a certain negative effect on the environment. Meanwhile, considerable copper and iron resources exist in the copper slag, and if the copper slag is not effectively recycled, great waste of strategic metal copper and iron resources is caused. According to statistics, about 2-3 tons of copper slag are produced in each 1 ton of copper produced in the copper pyrometallurgy process. According to the calculation, copper slag with the annual output of more than ten millions of tons is produced in China, and if the copper slag is not treated in time, heavy metals in the slag can be dissolved out into soil and rivers to cause secondary environmental pollution after long-term rain, wind blowing and the like. Therefore, the copper slag is impoverished and utilized with great significance. At present, the method for treating copper slag mainly comprises slow cooling flotation and pyrogenic dilution. The slow-cooling flotation process has the characteristics of low energy consumption and high recovery rate, and the slow-cooling flotation process has the advantages that the copper mineral particles in the obtained copper slag are coarse, partial coarse-particle copper mineral monomers can be dissociated by grinding in a short time, the slow-cooling flotation process is to carry out flotation on coarse-particle copper minerals which reach the flotation requirement to produce, and the pyrogenic depletion process is to add a reducing agent into the copper slag to carry out high-temperature smelting, so that the slag and copper are effectively separated, and copper metal is obtained. The patent with publication No. CN113186404A proposes a copper slag thermal state vortex depletion method, which is to load a stirrer into a copper slag layer to stir to form a vortex, so that the temperature field in a furnace is more uniform, the depletion reaction time is shortened, a depletion agent is added to carry out vortex depletion reaction, depletion slag contains about 0.22% of Cu by mass percent, the patent realizes the reinforcement of a reduction process by vortex stirring melt, and improves the metal recovery rate, the patent with publication No. CN108728664A proposes a method for reinforcing copper smelting slag depletion by waste iron oxide desulfurizing agent, the method is to mix the waste iron oxide desulfurizing agent and other reagents to prepare depletion agent pellets, and then to put the depletion agent pellets into a copper smelting slag depletion electric furnace to carry out depletion, so as to achieve the aim of waste treatment by waste, the obtained depletion slag contains less than 0.35% of Cu by weight, and the matte grade is more than 15% by weight. The two methods can recover copper resources in copper slag, but the copper content in the depleted slag is still more than 0.2%, and the method still has a larger recovery value. In the prior art, the processes of magnetic separation roughing, regrinding, magnetic separation concentration, reverse flotation and the like are mostly adopted to carry out ore dressing tests for recovering iron ore concentrate and coal dressing heavy media from copper slag copper tailings. A method for comprehensively recovering magnetite and copper minerals from copper slag flotation tailings as proposed in the patent publication No. CN109647616 a. Firstly, carrying out magnetic roughing, carrying out magnetic separation on copper slag flotation tailings under the condition of 1200 Gs and 2200Gs to respectively obtain magnetic roughing concentrate and magnetic tailings, carrying out shaking table gravity separation, respectively adding 450g/t550g/t water glass and 15g/t25g/t Z200, sending into a stirring barrel, stirring for 5min, carrying out regrinding and magnetic separation, merging the magnetic roughing concentrate and the shaking table concentrate, sending into a ball mill, regrinding, adding lime as a grinding aid, and finally carrying out flotation and recycling of copper minerals. The process is complex and has high energy consumption, and only magnetite concentrate is obtained. The existing copper slag recovery treatment process needs to add a strong oxidant for reduction reaction, and has the defects of high cost, complex process or impure iron powder obtained after recovery and separation, difficult recov