Method for producing nickel anode plate from industrial hazardous waste containing nickel and copper
Through drying, roasting, vulcanizing and smelting and blowing processes, the problem of low treatment efficiency of hazardous waste in nickel-containing copper industry is solved, and efficient recycling of valuable metals and resource-based and harmless treatment of waste is achieved.
Patent Information
- Application Number
- CN202510568686.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-30
- Publication Date
- 2025-07-25
AI Technical Summary
In the prior art, the treatment and recycling efficiency of hazardous wastes in nickel-containing copper industries is low, and the traditional process has problems such as long process flow, complexity, high energy consumption and low recovery rate of valuable metals.
The nickel anode plate is produced by using dry roasting, vulcanization smelting and blowing processes, through the steps of sorting ingredients, dry roasting, vulcanization smelting, blowing and grinding and sorting, and using gypsum slag as the vulcanizing agent, quartz as the flux, and pulverized coal as the reducing agent to achieve efficient recovery of valuable metals.
The comprehensive recycling of valuable metals in hazardous wastes in nickel-containing copper industry has been realized, and converted into general industrial solid waste, which has achieved resource utilization, harmlessness and reduced processing, and has improved the recycling rate of valuable metals.
Smart Images
Figure CN120366582A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of metal recycling and reuse, and particularly relates to a method for producing nickel anode plates from nickel- and copper-containing industrial hazardous waste. Background Art
[0002] Nickel- and copper-containing industrial hazardous waste mainly includes by-products such as sludge, leaching residues, neutralization residues, and acid muds produced by electroplating enterprises, nickel and copper hydrometallurgy enterprises, acid water treatment enterprises, and wastewater treatment enterprises through methods such as leaching, neutralization, adsorption, and electrolysis. This by-product contains a certain amount of valuable metals such as Ni, Cu, and Fe, and at the same time, it also contains a certain amount of Cr. According to relevant national environmental protection regulations, the stacking time of hazardous waste cannot exceed 1 year, and the treatment of industrial hazardous waste requires relevant qualifications. Therefore, most enterprises hand over hazardous waste to enterprises with industrial hazardous waste treatment qualifications. Hazardous waste treatment enterprises generally divide the submitted materials into two categories. One category is materials containing valuable metals such as Ni, Cu, and Fe, and the other category is materials without recyclable value. For materials without recyclable value, the landfill method is generally used for treatment. For materials containing valuable metals such as Ni, Cu, and Fe, the method of recovering valuable metals and then landfilling is generally used. Due to the large variety, fluctuating composition, and complex raw materials of materials containing valuable metals, the treatment difficulty is also very high. Using traditional hydrometallurgy processes has problems such as long process flow, complex processes, difficult wastewater treatment, and low recovery rate of valuable metals; using traditional pyrometallurgy processes has problems such as high energy consumption, low product added value, and low recovery rate of valuable metals. Summary of the Invention
[0003] The present invention provides a method for producing nickel anode plates from nickel- and copper-containing industrial hazardous waste to solve the problems existing in the above background.
[0004] To achieve the above object, the present invention adopts the following technical solutions: A method for producing nickel anode plates from nickel- and copper-containing industrial hazardous waste, comprising the following steps: Step 1: Classify and proportion the nickel- and copper-containing industrial hazardous waste raw materials according to the Ni, Cu, and Fe grades. After proportioning, the mixed material contains Ni + Cu ≥ 4%, Fe 15% - 50%, Cr 0.5% - 6%, and water 5% - 40%.
[0005] Step 2: Dry and roast the mixed material in Step 1 to produce calcine with water content ≤ 0.5%. The produced flue gas is collected by dust collection equipment and discharged up to standard, and the produced calcine is discharged into a high-temperature silo.
[0006] Step 3: Add the calcined ore produced in Step 2 to a smelting furnace after adding flux, reducing agent and sulfiding agent for smelting to produce matte with Ni+Cu≥20%. After converting the matte, produce high-grade matte with Ni+Cu≥65% and Fe≤3%, and cast it into high-grade matte blocks.
[0007] Step 4: Grind and float the high-grade matte blocks in Step 3 to produce nickel concentrate with Ni≥65% and Cu≤4%, and copper concentrate with Cu≥65% and Ni≤5%. After melting and casting the nickel concentrate, produce nickel anode plates.
[0008] Further, the nickel-copper industrial hazardous waste raw material in Step 1 contains 1.5%-25% Ni, 1.5%-8% Cu, 15%-50% Fe, 0.5%-5% Cr, and 5%-40% water.
[0009] Further, the sulfiding agent in Step 3 is gypsum slag from industrial solid waste.
[0010] Further, during the sulfide smelting process in Step 3, Cr with a content ≥95% in the raw material enters the smelting slag.
[0011] Further, the smelting slag produced in Step 3 is general industrial solid waste, which can realize the harmless and reduction treatment of industrial hazardous waste raw materials.
[0012] The present invention has the following beneficial effects: In the sulfide smelting process of the present invention, the sulfiding agent used is gypsum slag from industrial solid waste, the reducing agent used is C-based reducing agents such as pulverized coal, and the flux is quartz. Sulfur in the gypsum slag reacts with Ni, Cu, Fe, etc. in the raw material under the action of the carbon-based reducing agent and flux to produce nickel matte, i.e., a mixture of NiS, Cu2S, and FeS.
[0013] In the sulfide smelting process of the present invention, Cr, Fe in the raw material react with the carbon-based reducing agent and flux under high temperature to produce slag such as Cr2FeO4, Cr2MgO4, and CaSiO3. The produced slag has stable performance, meets national environmental protection requirements, and can be directly landfilled.
[0014] The present invention can realize the comprehensive recovery of valuable metals such as nickel and copper in nickel-copper industrial hazardous waste. At the same time, industrial hazardous waste can be converted into general industrial solid waste, realizing the resource utilization, harmlessness, and reduction treatment of nickel-copper industrial hazardous waste. Description of the Drawings
[0015] Figure 1 It is a process diagram for preparing nickel anode plates of the present invention. Detailed Embodiments
[0016] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
[0017] Example 1 A method for producing nickel anode plates from nickel-copper industrial hazardous waste, the key processes of the treatment process sequentially include: (1) Mixing and batching of nickel-copper waste: Mix and batch various nickel-copper wastes according to the grades of Ni, Cu, and Fe. After batching, the mixed material contains 1.5% Ni, 8% Cu, 35% Fe, 0.5% Cr, and 5% water.
[0018] (2) Drying and roasting of nickel-copper waste: The mixed material is dried at 280 °C for 5 min and roasted at 550 °C for 10 min to produce roasted ore with 0.5% water. The flue gas produced is dust-collected by dust collection equipment and discharged up to standard, and the produced roasted ore is discharged into a high-temperature bin.
[0019] (3) Sulfide smelting and converting of nickel-copper waste: For sulfide smelting, roasted ore, pulverized coal, quartz, and gypsum are added into a smelting furnace according to a mass ratio of 100:16:28:35, and smelted at 1350 °C for 1 h to produce low-grade nickel matte containing 3.77% Ni, 20.22% Cu, 15.09% Fe, 0.06% Cr, and 18.64% S; for converting, the low-grade nickel matte and quartz are converted at 1300 °C for 6 h according to a mass ratio of 100:9 to produce high-grade nickel matte containing 10.56% Ni, 56.58% Cu, 2.98% Fe, 0.01% Cr, and 19.86% S, and then cast into high-grade nickel matte blocks and slowly cooled.
[0020] (4) Grinding, flotation, and casting of high-grade nickel matte: After slow cooling, the high-grade nickel matte is subjected to grinding and flotation separation to produce nickel concentrate containing 65.50% Ni, 3.12% Cu, 2.46% Fe, 0.02% Cr, and 20.52% S, copper concentrate containing 66.20% Cu, 1.10% Ni, 3.18% Fe, 0.01% Cr, and 21.43% S. The nickel concentrate is smelted at 1250 °C for 40 min and then cast into nickel anode plates.
[0021] Example 2 A method for producing nickel anode plates from nickel-copper industrial hazardous waste, the key processes of the treatment process sequentially include: (1) Mixing and batching of nickel-copper waste: Mix and batch various nickel-copper wastes according to the grades of Ni, Cu, and Fe. After batching, the mixed material contains 2.5% Ni, 1.5% Cu, 15% Fe, 3% Cr, and 30% water.
[0022] (2) Drying and roasting of nickel- and copper-containing waste: The mixed material is dried at 280°C for 30 min and roasted at 550°C for 20 min to produce roasted ore with 0.4% water content. The flue gas produced is collected by dust collection equipment and discharged up to standard, and the produced roasted ore is discharged into a high-temperature bin.
[0023] (3) Sulfide smelting and converting of nickel- and copper-containing waste: For sulfide smelting, the roasted ore, pulverized coal, quartz, and gypsum are added into the smelting furnace according to the mass ratio of 100:7:14:36, and smelted at 1320°C for 1 h to produce low-grade nickel matte containing 14.03% Ni, 8.75% Cu, 21.74% Fe, 0.81% Cr, and 21.80% S. For converting, the low-grade nickel matte and quartz are converted at 1300°C for 6 h according to the mass ratio of 100:14 to produce high-grade nickel matte containing 40.68% Ni, 25.60% Cu, 2.98% Fe, 0.11% Cr, and 24.73% S, and then cast into high-grade nickel matte blocks for slow cooling.
[0024] (4) Grinding, flotation, and casting of high-grade nickel matte: After slow cooling, the high-grade nickel matte is subjected to grinding and flotation separation to produce nickel concentrate containing 65.09% Ni, 3.09% Cu, 2.23% Fe, and 23.30% S, and copper concentrate containing 66.56% Cu, 3.53% Ni, 3.44% Fe, and 25.72% S. The nickel concentrate is smelted at 1250°C for 40 min and then cast to produce nickel anode plates.
[0025] Example 3 A method for producing nickel anode plates from nickel- and copper-containing industrial hazardous waste, the key processes of the treatment process sequentially include: (1) Mixing and batching of nickel- and copper-containing waste: According to the grades of Ni, Cu, and Fe, various nickel- and copper-containing wastes are mixed and batched. After batching, the mixed material contains 25% Ni, 6.5% Cu, 50% Fe, 5% Cr, and 40% water.
[0026] (2) Drying and roasting of nickel- and copper-containing waste: The mixed material is dried at 280°C for 40 min and roasted at 550°C for 30 min to produce roasted ore with 0.3% water content. The flue gas produced is collected by dust collection equipment and discharged up to standard, and the produced roasted ore is discharged into a high-temperature bin.
[0027] (3) Sulfide smelting and converting of nickel-containing copper waste: For sulfide smelting, roasted ore, pulverized coal, quartz, and gypsum are added into the smelting furnace according to the mass ratio of 100:24:40:54, smelted at 1320 °C for 1 h to produce matte with Ni 11.08%, Cu 13.18%, Fe 21.39%, Cr 0.48%, and S 20.50%. For converting, the matte and quartz are converted at 1300 °C for 6 h according to the mass ratio of 100:13 to produce nickel matte with Ni 31.02%, Cu 37.03%, Fe 2.98%, Cr 0.06%, and S 22.67%, which is then cast into nickel matte blocks and slowly cooled.
[0028] (4) Grinding, flotation, and casting of nickel matte: After slow cooling, the nickel matte is subjected to grinding and flotation separation to produce nickel concentrate with Ni 65.14%, Cu 3.02%, Fe 2.29%, and S 23.80%, and copper concentrate with Cu 66.56%, Ni 4.34%, Fe 3.58%, and S 21.76%. The nickel concentrate is smelted at 1250 °C for 40 min and then cast to produce nickel anode plates.
Claims
1. A method for producing nickel anode plates from nickel-containing copper industrial hazardous waste, characterized in that, It includes the following steps: Step 1: Classify and proportion the raw materials of nickel and copper-containing industrial hazardous waste according to the grades of Ni, Cu, and Fe. After proportioning, the mixed material contains Ni + Cu ≥ 4%, Fe 15% - 50%, Cr 0.5% - 6%, and water 5% - 40%; Step 2: Dry and roast the mixed material in Step 1 to produce roasted ore with water content ≤ 0.5%. The flue gas produced is dust-collected by dust collection equipment and discharged up to the standard, and the produced roasted ore is discharged into a high-temperature bin; Step 3: Add the roasted ore produced in Step 2 into a smelting furnace after adding flux, reducing agent, and sulfiding agent for smelting to produce matte with Ni + Cu ≥ 20%. After the matte is blown, high-grade matte with Ni + Cu ≥ 65% and Fe ≤ 3% is produced and cast into high-grade matte blocks; Step 4: After grinding and flotation separation of the high-grade matte blocks in Step 3, nickel concentrate with Ni ≥ 65% and Cu ≤ 4% is produced, and copper concentrate with Cu ≥ 65% and Ni ≤ 5% is produced. The nickel concentrate is melted and cast to produce nickel anode plates.
2. The method for producing nickel anode plates from nickel-containing copper industrial hazardous waste according to claim 1, characterized in that: The raw materials of nickel and copper-containing industrial hazardous waste in Step 1 contain Ni 1.5% - 25%, Cu 1.5% - 8%, Fe 15% - 50%, Cr 0.5% - 5%, and water 5% - 40%.
3. A method for producing nickel anode plates from nickel-containing copper industrial hazardous waste according to claim 1, characterized in that: The sulfiding agent in Step 3 uses gypsum slag in industrial solid waste.
4. The method for producing nickel anode plates from nickel-containing copper industrial hazardous waste according to claim 1, characterized in that: During the sulfide smelting process in Step 3, Cr with a content ≥ 95% in the raw materials enters the smelting slag.