Copper-nickel alloy treatment method for realizing recycling of neutralizer

Abstract

The invention discloses a copper-nickel alloy treatment method for realizing recycling of a neutralizing agent. The copper-nickel alloy treatment method comprises the following steps: step 1, two-section countercurrent leaching; the first-section leachate obtained in the first step is neutralized through magnesium oxide and oxidized through air blowing, the neutralization temperature is 75-90 DEG C, the end point PH is controlled to be 2.5-4.0, and neutralized liquid and neutralized residues are obtained after filtration; 3, copper extraction, wherein magnesium soap p204 is adopted for extracting copper from the neutralized solution obtained in the step 2, and a copper sulfate solution and copper extraction raffinate are obtained; 4, nickel extraction is conducted, specifically, nickel extraction is conducted on the copper extraction raffinate obtained in the step 3 through magnesium soap HBL116, and a cobalt nickel sulfate solution and nickel extraction raffinate are obtained; step 5, evaporative crystallization: performing evaporative crystallization on the nickel raffinate obtained in the step 4 to obtain magnesium sulfate crystals, and recycling evaporated water; and step 6, calcining: calcining the magnesium sulfate crystal obtained in the step 5 at the calcining temperature of 1050-1200 DEG C for 1-3 hours to produce magnesium oxide and flue gas.

Description

Technical Field

[0001] The invention relates to the technical field of copper-nickel alloy wet treatment process, and in particular to a copper-nickel alloy treatment method for realizing the recycling of a neutralizing agent. Background Art

[0002] The copper concentrate is smelted in a self-heating furnace to obtain sulfur-containing crude copper, which is then blown through a Kaldo furnace to remove nickel, resulting in the Kaldo slag containing a large amount of copper and nickel (Cu30%-36%, Ni9%-15%). The Kaldo slag is reduced and smelted to produce a copper-nickel alloy intermediate product, which contains about 30% nickel and about 65% copper, and is a very good raw material for nickel and copper. The main methods for treating copper-nickel alloys at present include leaching in a sulfuric acid system (oxidized with hydrogen peroxide, sodium chlorate, etc.) and a nitric acid system. After leaching, copper and nickel are dissolved in the leachate and then recovered as corresponding products. However, the copper and nickel obtained by the above methods are not of high quality. Summary of the invention

[0003] In view of the above technical problems, the present invention provides a copper-nickel alloy treatment method for realizing the recycling of a neutralizing agent.

[0004] In order to achieve the above object, the technical solution of the present invention is as follows: A method for treating a copper-nickel alloy to realize recycling of a neutralizing agent comprises the following steps: Step 1, two-stage countercurrent leaching: leaching reaction is carried out on the copper-nickel alloy powder, air is blown for stirring, the reaction temperature is above 80°C, the reaction time is 4h-6h, and solid-liquid separation is carried out to obtain a first-stage leaching liquid and a first-stage leaching residue; sulfuric acid obtained from a flue gas acid-making system is continuously added to the first-stage leaching residue, the amount of sulfuric acid used is 1.0-1.1 times the theoretical amount of leached copper-nickel alloy powder, the liquid-solid ratio is controlled to be 10:1-15:1, air is blown for stirring, the reaction temperature is 80°C-90°C, and the leaching time is 4h-6h, and solid-liquid separation is carried out to obtain a second-stage leaching liquid and a second-stage leaching residue, wherein the second-stage leaching residue is returned to the process of producing copper-nickel alloy powder, and the second-stage leaching liquid enters the first-stage leaching to participate in the leaching reaction of the copper-nickel alloy powder; Step 2, neutralization: neutralize the first section of the leaching solution obtained in step 1 with magnesium oxide, oxidize with air, neutralize for 4h-6h, neutralize at 75°C-90°C, control the end point pH at 2.5-4.0, and obtain neutralized liquid and neutralized slag after filtration; Step 3, copper extraction: the neutralized solution obtained in step 2 is subjected to copper extraction using magnesium soap P204 to obtain a copper sulfate solution and a residual copper extraction solution; Step 4, nickel extraction: the copper extraction residual solution obtained in step 3 is subjected to nickel extraction using magnesium soap HBL116 to obtain a nickel cobalt sulfate solution and a nickel extraction residual solution; Step 5, evaporation and crystallization: evaporating and crystallizing the nickel raffinate obtained in step 4 to obtain magnesium sulfate crystals, and evaporating water for reuse; Step 6, calcination: calcine the magnesium sulfate crystals obtained in step 5 at a calcination temperature of 1050°C-1200°C for 1h-3h to produce magnesium oxide and flue gas. The flue gas is returned to the existing acid production system to produce sulfuric acid, and the magnesium oxide is used in the neutralization and saponification processes.

[0005] The production method of P204 magnesium soap comprises: mixing and stirring the magnesium oxide obtained in step 6 with water to obtain a magnesium oxide slurry with a mass concentration of 5%-20%, mixing and stirring the magnesium oxide slurry with a P204 organic with a concentration of 15%-25% for 3-8 minutes, the reaction temperature is 25°C-35°C, the saponification rate is 60%-70%, and after the saponification reaction is completed, the phase separation is allowed to stand to obtain magnesium soap P204 organic and P204 saponified liquid.

[0006] Wherein, the P204 magnesium soap copper extraction comprises: copper extraction - nickel washing - back extraction - iron washing steps; Among them, copper extraction: the extraction phase ratio O / A is 3-6:1, and the extraction level is 4-6; nickel washing: the p204 loading nickel washing level is 4-6, the nickel washing phase ratio is 6-10:1, and sulfuric acid solution is used to wash nickel; back extraction: sulfuric acid solution is back extracted to obtain copper sulfate solution, and the back extraction sulfuric acid concentration is 80g / L-130g / L; iron washing: 6mol / L-8mol / L hydrochloric acid is used to wash iron.

[0007] The production method of HBL116 magnesium soap comprises: mixing and stirring the magnesium oxide obtained in step 6 with water to obtain a magnesium oxide slurry with a mass concentration of 5%-20%, mixing and stirring the magnesium oxide slurry with a concentration of 30%-40% HBL116 organic for reaction for 3-8 minutes, the saponification temperature is 25°C-35°C, the saponification rate is 60%-80%, and after the saponification reaction is completed, the phase separation is allowed to stand to obtain magnesium soap HBL116 organic and HBL116 saponified liquid.

[0008] Wherein, the HBL116 magnesium soap nickel extraction includes: nickel extraction-magnesium washing-strip extraction-organic regeneration process; Among them, nickel extraction: the extraction phase ratio O / A is 4-8:1, the extraction stage is 4-6, the extraction reaction time is 3-5min, and the extraction temperature is 25℃-35℃; magnesium washing: HBL116 is loaded with 4-6 magnesium washing stages, the magnesium washing phase ratio is 6-10:1, and sulfuric acid solution is used for magnesium washing; stripping: sulfuric acid solution stripping obtains nickel cobalt sulfate solution, the stripping sulfuric acid concentration is 0.5-0.7mol / L, and a two-stripping process is adopted; organic regeneration: 0.5mol / L-0.7mol / L sulfuric acid solution regenerates organic HBL116.

[0009] Among them, the copper-nickel alloy comes from the copper-nickel alloy powder obtained by reduction smelting of copper smelting Kaldo furnace slag, wherein the copper content is 50%-75%, the nickel content is 25%-50%, and the iron content is 0.25%-1.0%. The copper-nickel alloy adopts two-stage countercurrent sulfuric acid leaching, and the leaching slag rate is 2%-3%. The leaching slag can be returned to the previous reduction smelting process to recycle the valuable metals such as nickel and copper therein.

[0010] Among them, the water phase produced during the saponification process of p204 and HBL116 in the saponification process in step 2 is returned to the saponification process to continue to prepare magnesium oxide slurry or returned to the leaching system for water replenishment.

[0011] Among them, the copper-nickel alloy leaching agent is sulfuric acid, and the alkali used for saponification in the process of neutralizing and extracting the leaching solution to recover copper and nickel respectively is magnesium oxide, and finally a magnesium sulfate solution is obtained. The crystallization-calcination process is used to realize the recycling of magnesium oxide and water, and the output flue gas is connected to the existing copper smelting flue gas acid production system to obtain sulfuric acid again, and the entire process realizes the recycling of the leaching agent.

[0012] The beneficial effects of the present invention are as follows: the present invention performs wet treatment on copper-nickel alloy obtained by reduction smelting of Kaldor slag produced by the copper smelting system to obtain copper sulfate solution and nickel-cobalt sulfate solution, thereby realizing the recovery of valuable metals in the copper-nickel alloy. The entire process is in a sulfuric acid system, and magnesium oxide is used as a neutralizing agent and saponifying agent, thereby realizing the recycling of alkali and acid in the process of copper, nickel and cobalt recovery in the whole process. The entire process has no wastewater output, and is a green and environmentally friendly metallurgical process. The present invention extracts and separates to obtain copper sulfate solution, which can be directly connected to the next step of copper recovery (electrolytic copper, crystallized copper sulfate); extracts and separates to obtain nickel-cobalt sulfate solution, which can be directly connected to the next step of nickel recovery (electrolytic nickel or nickel sulfate product). The extracting saponifying agent in the present invention is 5%-20% magnesium oxide slurry, and the saponification rate, saponification temperature and other conditions are controlled to realize the saponification reaction between the slurry and the organic. The reaction is carried out in a stirred reactor. After the single-stage stirring reaction, the oil-water separation is placed in the phase separation system to obtain organic and saponified liquid after soap. The organic after soap is used for extraction, and the saponified liquid is returned to prepare magnesium oxide for recycling (or returned to the front leaching process for water replenishment). The present invention adopts HBL116 extractant, and HBL116 is used to extract nickel and cobalt in the magnesium sulfate system after being saponified with magnesium oxide, so as to realize the synchronous recovery of nickel and cobalt valuable metals, and lay the foundation for the copper-nickel alloy sulfuric acid leachate to use magnesium oxide as a neutralizing agent and realize the alkali and leaching agent reuse process. The copper-nickel alloy of the present invention comes from the reduction smelting of copper smelting Kaldo slag, and adopts a two-stage countercurrent leaching-neutralization-extraction separation of copper and nickel-magnesium oxide and sulfuric acid regeneration process to obtain copper sulfate solution and nickel-cobalt sulfate solution, so as to realize the recovery of valuable metals in the copper-nickel alloy. The entire process uses magnesium oxide as a neutralizing agent and saponifying agent under a sulfuric acid system, realizing the recycling of alkali and acid during the recovery of copper, nickel and cobalt in the entire process. The entire process does not produce any wastewater, making it a green and environmentally friendly metallurgical process. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The present invention is further described below in conjunction with the accompanying drawings and embodiments: Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0014] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present invention.

[0015] Example 1 like Figure 1 As shown, a copper-nickel alloy treatment method for realizing recycling of a neutralizer comprises the following steps: Step 1, two-stage countercurrent leaching: leaching reaction is carried out on the copper-nickel alloy powder, air is blown for stirring, the reaction temperature is above 80°C, the reaction time is 4 hours, and solid-liquid separation is carried out to obtain a first-stage leaching liquid and a first-stage leaching residue; sulfuric acid obtained from a flue gas acid-making system is continuously added to the first-stage leaching residue, the amount of sulfuric acid used is 1.0 times the theoretical amount of leached copper-nickel alloy powder, the liquid-solid ratio is controlled to be 10:1, air is blown for stirring, the reaction temperature is 80°C, and the leaching time is 4 hours, and solid-liquid separation is carried out to obtain a second-stage leaching liquid and a second-stage leaching residue, wherein the second-stage leaching residue is returned to the process of producing copper-nickel alloy powder, and the second-stage leaching liquid enters the first-stage leaching to participate in the leaching reaction of the copper-nickel alloy powder; Step 2, neutralization: neutralize the first section of the leaching solution obtained in step 1 with magnesium oxide, oxidize with air, neutralize for 4 hours, neutralize at 75°C, control the end point pH to 2.5, and obtain neutralized liquid and neutralized slag after filtration; Step 3, copper extraction: the neutralized solution obtained in step 2 is subjected to copper extraction using magnesium soap P204 to obtain a copper sulfate solution and a residual copper extraction solution; Step 4, nickel extraction: the copper extraction residual solution obtained in step 3 is subjected to nickel extraction using magnesium soap HBL116 to obtain a nickel cobalt sulfate solution and a nickel extraction residual solution; Step 5, evaporation and crystallization: evaporating and crystallizing the nickel raffinate obtained in step 4 to obtain magnesium sulfate crystals, and evaporating water for reuse; Step 6, calcination: calcine the magnesium sulfate crystals obtained in step 5 at a calcination temperature of 1050°C for 1 hour to produce magnesium oxide and flue gas. The flue gas is returned to the existing acid production system to produce sulfuric acid, and the magnesium oxide is used in the neutralization and saponification processes.

[0016] The production method of P204 magnesium soap comprises: mixing and stirring the magnesium oxide obtained in step 6 with water to obtain a magnesium oxide slurry with a mass concentration of 5%, mixing and stirring the magnesium oxide slurry with a P204 organic with a concentration of 15% for 3 minutes, the reaction temperature is 25° C., the saponification rate is 60%, and after the saponification reaction is completed, the phase separation is allowed to stand to obtain magnesium soap P204 organic and P204 saponified liquid.

[0017] Wherein, the P204 magnesium soap copper extraction comprises: copper extraction - nickel washing - back extraction - iron washing steps; Among them, copper extraction: the extraction phase ratio O / A is 3:1, and the extraction level is 4; nickel washing: p204 load nickel washing level is 4, the nickel washing phase ratio is 6:1, and sulfuric acid solution is used to wash nickel; back extraction: sulfuric acid solution is back-extracted to obtain copper sulfate solution, and the back-extraction sulfuric acid concentration is 80g / L; iron washing: 6mol / L hydrochloric acid is used to wash iron.

[0018] The production method of HBL116 magnesium soap comprises: mixing and stirring the magnesium oxide obtained in step 6 with water to obtain a magnesium oxide slurry with a mass concentration of 5%, mixing and stirring the magnesium oxide slurry with a HBL116 organic with a concentration of 30% for 3 minutes, the saponification temperature is 25° C., the saponification rate is 60%, and after the saponification reaction is completed, standing and phase separation is performed to obtain magnesium soap HBL116 organic and HBL116 saponified liquid.

[0019] Wherein, the HBL116 magnesium soap nickel extraction includes: nickel extraction-magnesium washing-strip extraction-organic regeneration process; Among them, nickel extraction: the extraction phase ratio O / A is 4:1, the extraction stage is 4, the extraction reaction time is 3min, and the extraction temperature is 25°C; magnesium washing: HBL116 is loaded with 4 levels of magnesium washing, the magnesium washing phase ratio is 6:1, and sulfuric acid solution is used to wash magnesium; stripping: sulfuric acid solution stripping obtains nickel cobalt sulfate solution, the stripping sulfuric acid concentration is 0.5 mol / L, and a two-time stripping process is adopted; organic regeneration: 0.5 mol / L sulfuric acid solution regenerates organic HBL116.

[0020] Among them, the copper-nickel alloy comes from the copper-nickel alloy powder obtained by reduction smelting of copper smelting Kaldo furnace slag, wherein the copper content is 50%-75%, the nickel content is 25%-50%, and the iron content is 0.25%-1.0%. The copper-nickel alloy adopts two-stage countercurrent sulfuric acid leaching, and the leaching slag rate is 2%-3%. The leaching slag can be returned to the previous reduction smelting process to recycle the valuable metals such as nickel and copper therein.

[0021] Among them, the water phase produced during the saponification process of p204 and HBL116 in the saponification process in step 2 is returned to the saponification process to continue to prepare magnesium oxide slurry or returned to the leaching system for water replenishment.

[0022] Among them, the copper-nickel alloy leaching agent is sulfuric acid, and the alkali used for saponification in the process of neutralizing and extracting the leaching solution to recover copper and nickel respectively is magnesium oxide, and finally a magnesium sulfate solution is obtained. The crystallization-calcination process is used to realize the recycling of magnesium oxide and water, and the output flue gas is connected to the existing copper smelting flue gas acid production system to obtain sulfuric acid again, and the entire process realizes the recycling of the leaching agent.

[0023] Example 2 like Figure 1 As shown, a copper-nickel alloy treatment method for realizing recycling of a neutralizer comprises the following steps: Step 1, two-stage countercurrent leaching: leaching reaction is carried out on the copper-nickel alloy powder, air is blown for stirring, the reaction temperature is above 80°C, the reaction time is 6 hours, and solid-liquid separation is carried out to obtain a first-stage leaching liquid and a first-stage leaching residue; sulfuric acid obtained from a flue gas acid-making system is continuously added to the first-stage leaching residue, the amount of sulfuric acid used is 1.1 times the theoretical amount of leached copper-nickel alloy powder, the liquid-solid ratio is controlled to be 15:1, air is blown for stirring, the reaction temperature is 90°C, and the leaching time is 6 hours, and solid-liquid separation is carried out to obtain a second-stage leaching liquid and a second-stage leaching residue, wherein the second-stage leaching residue is returned to the process of producing copper-nickel alloy powder, and the second-stage leaching liquid enters the first-stage leaching to participate in the leaching reaction of the copper-nickel alloy powder; Step 2, neutralization: neutralize the first section of the leaching solution obtained in step 1 with magnesium oxide, oxidize with air, neutralize for 6 hours, neutralize at 90°C, control the end point pH to 4.0, and obtain neutralized liquid and neutralized slag after filtration; Step 3, copper extraction: the neutralized solution obtained in step 2 is subjected to copper extraction using magnesium soap P204 to obtain a copper sulfate solution and a residual copper extraction solution; Step 4, nickel extraction: the copper extraction residual solution obtained in step 3 is subjected to nickel extraction using magnesium soap HBL116 to obtain a nickel cobalt sulfate solution and a nickel extraction residual solution; Step 5, evaporation and crystallization: evaporating and crystallizing the nickel raffinate obtained in step 4 to obtain magnesium sulfate crystals, and evaporating water for reuse; Step 6, calcination: calcine the magnesium sulfate crystals obtained in step 5 at a calcination temperature of 1200°C for 3 hours to produce magnesium oxide and flue gas. The flue gas is returned to the existing acid production system to produce sulfuric acid, and the magnesium oxide is used in the neutralization and saponification processes.

[0024] The production method of P204 magnesium soap comprises: mixing and stirring the magnesium oxide obtained in step 6 with water to obtain a magnesium oxide slurry with a mass concentration of 20%, mixing and stirring the magnesium oxide slurry with a P204 organic with a concentration of 25% for 8 minutes, the reaction temperature is 35° C., the saponification rate is 70%, and after the saponification reaction is completed, the phase separation is allowed to stand to obtain the magnesium soap P204 organic and the P204 saponified liquid.

[0025] Wherein, the P204 magnesium soap copper extraction comprises: copper extraction - nickel washing - back extraction - iron washing steps; Among them, copper extraction: the extraction phase ratio O / A is 6:1, and the extraction level is 6; nickel washing: p204 load nickel washing level is 6, the nickel washing phase ratio is 10:1, and sulfuric acid solution is used to wash nickel; back extraction: sulfuric acid solution is back-extracted to obtain copper sulfate solution, and the back-extraction sulfuric acid concentration is 130g / L; iron washing: 8mol / L hydrochloric acid is used to wash iron.

[0026] The production method of HBL116 magnesium soap comprises: mixing and stirring the magnesium oxide obtained in step 6 with water to obtain a magnesium oxide slurry with a mass concentration of 20%, mixing and stirring the magnesium oxide slurry with a HBL116 organic with a concentration of 40% for 8 minutes, the saponification temperature is 35° C., the saponification rate is 80%, and after the saponification reaction is completed, the phase separation is allowed to stand to obtain magnesium soap HBL116 organic and HBL116 saponified liquid.

[0027] Wherein, the HBL116 magnesium soap nickel extraction includes: nickel extraction-magnesium washing-strip extraction-organic regeneration process; Among them, nickel extraction: the extraction phase ratio O / A is 8:1, the extraction stage is 6, the extraction reaction time is 5min, and the extraction temperature is 35°C; magnesium washing: HBL116 is loaded with 6 levels of magnesium washing, the magnesium washing phase ratio is 10:1, and sulfuric acid solution is used for magnesium washing; stripping: sulfuric acid solution stripping obtains nickel cobalt sulfate solution, the stripping sulfuric acid concentration is 0.7 mol / L, and a two-time stripping process is adopted; organic regeneration: 0.7 mol / L sulfuric acid solution regenerates organic HBL116.

[0028] Among them, the copper-nickel alloy comes from the copper-nickel alloy powder obtained by reduction smelting of copper smelting Kaldo furnace slag, wherein the copper content is 50%-75%, the nickel content is 25%-50%, and the iron content is 0.25%-1.0%. The copper-nickel alloy adopts two-stage countercurrent sulfuric acid leaching, and the leaching slag rate is 2%-3%. The leaching slag can be returned to the previous reduction smelting process to recycle the valuable metals such as nickel and copper therein.

[0029] Among them, the water phase produced during the saponification process of p204 and HBL116 in the saponification process in step 2 is returned to the saponification process to continue to prepare magnesium oxide slurry or returned to the leaching system for water replenishment.

[0030] Among them, the copper-nickel alloy leaching agent is sulfuric acid, and the alkali used for saponification in the process of neutralizing and extracting the leaching solution to recover copper and nickel respectively is magnesium oxide, and finally a magnesium sulfate solution is obtained. The crystallization-calcination process is used to realize the recycling of magnesium oxide and water, and the output flue gas is connected to the existing copper smelting flue gas acid production system to obtain sulfuric acid again, and the entire process realizes the recycling of the leaching agent.

[0031] Example 3 Table 1 Main components of the copper-nickel alloy powder used in Example 3 (%) , Specific implementation process: add copper-nickel alloy to the second-stage leaching solution, heat, blow air, stir and react at 80°C. After reacting for 6 hours, measure the pH value to be 2.5, separate the solid and liquid, and obtain a first-stage atmospheric pressure leaching solution; add water and 1.0 times the theoretical amount of sulfuric acid to the first-stage atmospheric pressure leaching residue for second-stage atmospheric pressure leaching, control the liquid-solid ratio to 15:1, temperature to 80°C, blow air and stir to react for 6 hours, filter to obtain the second-stage leaching residue (return to the pyrometallurgical reduction smelting process) and the second-stage leaching solution (return to the first-stage leaching process); the first-stage atmospheric pressure leaching solution is poured into the neutralization reactor, heated, blow air, stirred, and a certain amount of magnesium oxide slurry is added. The neutralization reaction time is 4 hours, the temperature is 80°C, the neutralization endpoint pH is controlled to be 3.5, and the neutralization residue and the neutralized liquid are filtered; the neutralized liquid uses magnesium soap P204 to extract copper, the extraction ratio O / A is 6:1, and six-stage countercurrent extraction is performed to obtain the loaded P204 and the copper raffinate. The loaded P204 uses 0.1 mol / L sulfuric acid solution is used for four-stage countercurrent washing of nickel. After washing nickel, P204 loaded with nickel is stripped with 1.2mol / L sulfuric acid solution to obtain stripped copper sulfate solution; the copper extract residue is further subjected to magnesium soap HBL116 for nickel and cobalt extraction, and the extraction phase O / A ratio is 6:1, and four-stage countercurrent extraction is performed to obtain HBL116 loaded and nickel extracted residue solution, and HBL116 loaded with magnesium is used for four-stage countercurrent washing of magnesium with 0.03mol / L sulfuric acid solution. After washing magnesium, HBL116 loaded with magnesium is stripped with 0.5mol / L sulfuric acid solution to obtain stripped nickel sulfate solution, and the nickel sulfate obtained by stripping is further added with sulfuric acid to prepare a sulfuric acid concentration of 0.7mol / L, and the HBL116 loaded with nickel and cobalt is stripped again to obtain a stripped solution of nickel sulfate and cobalt solution; the nickel extracted residue is evaporated and crystallized to obtain magnesium sulfate crystals, which are calcined at a temperature of 1100°C for 3h to obtain magnesium oxide (return to the neutralization and magnesium soap process), and the flue gas is sent to the existing acid production system.

[0032] Organic saponification: P204 concentration is 20%, P204 organic and 15% magnesium oxide slurry are mixed and reacted for 8 minutes and then separated, the saponification temperature is 30°C, the saponification rate is 65%, and magnesium soap P204 is obtained for copper extraction; 40% HBL116 organic and 10% magnesium oxide slurry are mixed and reacted for 5 minutes and then separated, the saponification temperature is 35°C, the saponification rate is 70%, and magnesium soap HBL116 is obtained for nickel and cobalt extraction.

[0033] The compositions of the copper sulfate and nickel cobalt sulfate solutions are shown in Table 2.

[0034] Table 2 Main components of copper sulfate and nickel cobalt sulfate solutions obtained in Example 3 / g / L .

[0035] Example 4 Table 3 Main components of the copper-nickel alloy powder used in Example 4 (%) , Specific implementation process: add copper-nickel alloy to the second-stage leaching solution, heat, blow air, stir and react at 80°C. After reacting for 6 hours, measure the pH to be 2.0, separate the solid and liquid, and obtain a first-stage atmospheric pressure leaching solution; add water and 1.05 times the theoretical amount of sulfuric acid to the first-stage atmospheric pressure leaching residue for second-stage atmospheric pressure leaching, control the liquid-solid ratio to 12:1, the temperature to 85°C, blow air and stir to react for 5 hours, filter to obtain the second-stage leaching residue (return to the pyrometallurgical reduction smelting process) and the second-stage leaching solution (return to the first-stage leaching process); the first-stage atmospheric pressure leaching solution is poured into the neutralization reactor, heated, blow air, stirred, and a certain amount of magnesium oxide slurry is added. The neutralization reaction time is 5 hours, the temperature is 85°C, the neutralization endpoint pH is controlled to be 3.8, and the neutralization residue and the neutralized liquid are filtered; the neutralized liquid uses magnesium soap P204 to extract copper, the extraction phase O / A ratio is 5:1, and four-stage countercurrent extraction is performed to obtain the loaded P204 and the copper raffinate. The loaded P204 uses 0.1 The nickel is washed with 2mol / L sulfuric acid solution in four stages of countercurrent, and after washing the nickel, the loaded P204 is stripped with 1.2mol / L sulfuric acid solution to obtain a stripped copper sulfate solution; the copper extract residue is further extracted with magnesium soap HBL116 for nickel and cobalt extraction, and the extraction phase O / A ratio is 7:1, and six stages of countercurrent extraction are performed to obtain HBL116 and nickel extraction residue solution, and the loaded HBL116 is subjected to four stages of countercurrent washing of magnesium with 0.025mol / L sulfuric acid solution. After washing the magnesium, the loaded HBL116 is stripped with 0.6mol / L sulfuric acid solution to obtain a stripped nickel sulfate solution, and the nickel sulfate obtained by stripping is further added with sulfuric acid to prepare a sulfuric acid concentration of 0.6mol / L, and the HBL116 loaded with nickel and cobalt is stripped again to obtain a stripped nickel sulfate solution; the nickel extraction residue is evaporated and crystallized to obtain magnesium sulfate crystals, which are calcined at a temperature of 1150°C for 2h to obtain magnesium oxide (return to the neutralization and magnesium soap process), and the flue gas is sent to the existing acid production system.

[0036] Organic saponification: P204 concentration is 20%, P204 organic and 10% magnesium oxide slurry are mixed and reacted for 8 minutes and then separated, the saponification temperature is 25°C, the saponification rate is 70%, and magnesium soap P204 is obtained for copper extraction; 38% HBL116 organic and 5% magnesium oxide slurry are mixed and reacted for 8 minutes and then separated, the saponification temperature is 35°C, the saponification rate is 70%, and magnesium soap HBL116 is obtained for nickel and cobalt extraction.

[0037] The compositions of the copper sulfate and nickel cobalt sulfate solutions are shown in Table 2.

[0038] Table 4 Main components of copper sulfate and nickel cobalt sulfate solutions obtained in Example 4 / g / L .

[0039] Example 5 Table 5 Main components of the copper-nickel alloy powder used in Example 5 (%) , Specific implementation process: add copper-nickel alloy to the second-stage leaching solution, heat, blow air, stir and react at 80°C. After reacting for 6 hours, measure the pH value to be 2.0, separate the solid and liquid, and obtain a first-stage atmospheric pressure leaching solution; add water and 1.1 times the theoretical amount of sulfuric acid to the first-stage atmospheric pressure leaching residue for second-stage atmospheric pressure leaching, control the liquid-solid ratio to 10:1, the temperature to 90°C, blow air and stir to react for 4 hours, filter to obtain the second-stage leaching residue (return to the pyrometallurgical reduction smelting process) and the second-stage leaching solution (return to the first-stage leaching process); the first-stage atmospheric pressure leaching solution is poured into the neutralization reactor, heated, blow air, stirred, and a certain amount of magnesium oxide slurry is added. The neutralization reaction time is 4 hours, the temperature is 90°C, the neutralization endpoint pH is controlled to be 3.5, and the neutralization residue and the neutralized liquid are filtered; the neutralized liquid uses magnesium soap P204 to extract copper, the extraction ratio O / A is 8:1, and five-stage countercurrent extraction is performed to obtain the loaded P204 and the copper raffinate. The loaded P204 uses 0.2 mol / L sulfuric acid solution is used to countercurrently wash nickel for six stages. After washing nickel, P204 loaded with nickel is stripped with 1.2mol / L sulfuric acid solution to obtain stripped copper sulfate solution. The copper raffinate is further stripped with magnesium soap HBL116, and the extraction ratio O / A is 8:1. Five-stage countercurrent extraction is performed to obtain HBL116 loaded and nickel-extracted raffinate. The HBL116 loaded with magnesium is stripped with 0.025mol / L sulfuric acid solution for five stages. After washing magnesium, the HBL116 loaded with magnesium is stripped with 0.7mol / L sulfuric acid solution to obtain stripped nickel sulfate solution. The nickel sulfate obtained by stripping is further added with sulfuric acid to prepare a sulfuric acid concentration of 0.7mol / L, and the HBL116 loaded with nickel and cobalt is stripped again to obtain a stripped nickel sulfate solution. The nickel-extracted raffinate is evaporated and crystallized to obtain magnesium sulfate crystals, which are calcined at a temperature of 1200°C for 1h to obtain magnesium oxide (return to the neutralization and magnesium soap process), and the flue gas is sent to the existing acid production system.

[0040] Organic saponification: P204 concentration is 25%, P204 organic and 10% magnesium oxide slurry are mixed and reacted for 8 minutes and then separated, the saponification temperature is 25°C, the saponification rate is 50%, and magnesium soap P204 is obtained for copper extraction; 40% HBL116 organic and 10% magnesium oxide slurry are mixed and reacted for 8 minutes and then separated, the saponification temperature is 35°C, the saponification rate is 70%, and magnesium soap HBL116 is obtained for nickel and cobalt extraction.

[0041] The compositions of the copper sulfate and nickel cobalt sulfate solutions are shown in Table 6.

[0042] Table 6 Main components of copper sulfate and nickel cobalt sulfate solutions obtained in Example 5 / g / L .

[0043] It should be understood that the above specific embodiments of the present invention are only used to illustrate or explain the principles of the present invention, and do not constitute a limitation of the present invention. Therefore, any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. In addition, the appended claims of the present invention are intended to cover all changes and modifications that fall within the scope and boundaries of the appended claims, or the equivalent forms of such scope and boundaries.

Claims

1. A method for treating a copper-nickel alloy by recycling a neutralizing agent, characterized in that: The following steps are involved: Step 1, two-stage countercurrent leaching: leaching reaction is carried out on the copper-nickel alloy powder, air is blown for stirring, the reaction temperature is above 80°C, the reaction time is 4h-6h, and solid-liquid separation is carried out to obtain a first-stage leaching liquid and a first-stage leaching residue; sulfuric acid obtained from a flue gas acid-making system is continuously added to the first-stage leaching residue, the amount of sulfuric acid used is 1.0-1.1 times the theoretical amount of leached copper-nickel alloy powder, the liquid-solid ratio is controlled to be 10:1-15:1, air is blown for stirring, the reaction temperature is 80°C-90°C, and the leaching time is 4h-6h, and solid-liquid separation is carried out to obtain a second-stage leaching liquid and a second-stage leaching residue, wherein the second-stage leaching residue is returned to the process of producing copper-nickel alloy powder, and the second-stage leaching liquid enters the first-stage leaching to participate in the leaching reaction of the copper-nickel alloy powder; Step 2, neutralization: neutralize the first section of the leaching solution obtained in step 1 with magnesium oxide, oxidize with air, neutralize for 4h-6h, neutralize at 75°C-90°C, control the end point pH at 2.5-4.0, and obtain neutralized liquid and neutralized slag after filtration; Step 3, copper extraction: the neutralized solution obtained in step 2 is subjected to copper extraction using magnesium soap P204 to obtain a copper sulfate solution and a residual copper extraction solution; Step 4, nickel extraction: the copper extraction residual solution obtained in step 3 is subjected to nickel extraction using magnesium soap HBL116 to obtain a nickel cobalt sulfate solution and a nickel extraction residual solution; Step 5, evaporation and crystallization: evaporating and crystallizing the nickel raffinate obtained in step 4 to obtain magnesium sulfate crystals, and evaporating water for reuse; Step 6, calcination: calcine the magnesium sulfate crystals obtained in step 5 at a calcination temperature of 1050°C-1200°C for 1h-3h to produce magnesium oxide and flue gas. The flue gas is returned to the existing acid production system to produce sulfuric acid, and the magnesium oxide is used in the neutralization and saponification processes.

2. A method for treating a copper-nickel alloy for realizing recycling of a neutralizing agent according to claim 1, characterized in that: The production method of P204 magnesium soap comprises: mixing and stirring the magnesium oxide obtained in step 6 with water to obtain magnesium oxide slurry with a mass concentration of 5%-20%, mixing and stirring the magnesium oxide slurry with P204 organic with a concentration of 15%-25% for 3-8 minutes, the reaction temperature is 25°C-35°C, the saponification rate is 60%-70%, and after the saponification reaction is completed, the phase separation is allowed to stand to obtain magnesium soap P204 organic and P204 saponified liquid.

3. A method for treating a copper-nickel alloy for realizing recycling of a neutralizing agent according to claim 1, characterized in that: The p204 magnesium soap copper extraction comprises: copper extraction-nickel washing-reverse extraction-iron washing steps; Among them, copper extraction: the extraction phase ratio O / A is 3-6:1, and the extraction level is 4-6; nickel washing: the p204 loading nickel washing level is 4-6, the nickel washing phase ratio is 6-10:1, and sulfuric acid solution is used to wash nickel; back extraction: sulfuric acid solution is back extracted to obtain copper sulfate solution, and the back extraction sulfuric acid concentration is 80g / L-130g / L; iron washing: 6mol / L-8mol / L hydrochloric acid is used to wash iron.

4. A method for treating a copper-nickel alloy for realizing recycling of a neutralizing agent according to claim 1, characterized in that: The production method of HBL116 magnesium soap comprises: mixing and stirring the magnesium oxide obtained in step 6 with water to obtain magnesium oxide slurry with a mass concentration of 5%-20%, mixing and stirring the magnesium oxide slurry with HBL116 organic with a concentration of 30%-40% for 3-8 minutes, the saponification temperature is 25°C-35°C, the saponification rate is 60%-80%, and after the saponification reaction is completed, standing and separating the phases to obtain magnesium soap HBL116 organic and HBL116 saponified liquid.

5. A method for treating copper-nickel alloys for realizing recycling of neutralizing agents according to claim 1, characterized in that: The HBL116 magnesium soap nickel extraction includes: nickel extraction-magnesium washing-strip extraction-organic regeneration process; Among them, nickel extraction: the extraction phase ratio O / A is 4-8:1, the extraction stage is 4-6, the extraction reaction time is 3-5min, and the extraction temperature is 25℃-35℃; magnesium washing: HBL116 is loaded with 4-6 magnesium washing stages, the magnesium washing phase ratio is 6-10:1, and sulfuric acid solution is used for magnesium washing; stripping: sulfuric acid solution stripping obtains nickel cobalt sulfate solution, the stripping sulfuric acid concentration is 0.5-0.7mol / L, and a two-stripping process is adopted; organic regeneration: 0.5mol / L-0.7mol / L sulfuric acid solution regenerates organic HBL116.

6. A method for treating a copper-nickel alloy for realizing recycling of a neutralizing agent according to claim 1, characterized in that: The copper-nickel alloy comes from copper-nickel alloy powder obtained by reduction smelting of copper smelting Kaldo furnace slag, wherein the copper content is 50%-75%, the nickel content is 25%-50%, and the iron content is 0.25%-1.0%. The copper-nickel alloy is leached by two-stage countercurrent sulfuric acid, and the leaching slag rate is 2%-3%. The leaching slag can be returned to the previous reduction smelting process to recycle the valuable metals such as nickel and copper therein.

7. A method for treating a copper-nickel alloy for realizing recycling of a neutralizing agent according to claim 1, characterized in that: The water phase produced during the saponification process of p204 and HBL116 in the saponification process of step 2 is returned to the saponification process to continue to prepare magnesium oxide slurry or returned to the leaching system for water replenishment.

8. A method for treating a copper-nickel alloy for realizing recycling of a neutralizing agent according to claim 1, characterized in that: The copper-nickel alloy leaching agent is sulfuric acid, and the alkali used for saponification in the process of neutralizing and extracting the leaching solution to recover copper and nickel respectively is magnesium oxide, and finally a magnesium sulfate solution is obtained. The magnesium oxide and water are reused through a crystallization-calcination process, and the output flue gas is connected to the existing copper smelting flue gas acid-making system to obtain sulfuric acid again, and the entire process realizes the reuse of the leaching agent.

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