Method for comprehensively utilizing P204 strip liquor

Abstract

The invention discloses a comprehensive utilization method of a P204 strip liquor, which comprises the following steps: carrying out oil removal treatment on the P204 strip liquor to obtain an oil-removed liquor; carrying out primary alkali adjustment on the oil-removed liquid to obtain a primary alkali-adjusted liquid; carrying out acid pickling on the crude copper sulfide by utilizing the primary alkali adjusting solution to obtain washed copper sulfide and an acid pickling solution; carrying out secondary alkali regulation on the pickling solution to obtain a secondary alkali regulation solution and crude copper hydroxide; sulfide is added into the secondary alkali adjustment liquid for a copper deposition reaction, and liquid obtained after copper deposition and crude copper sulfide are obtained; adding sulfate into the solution after copper precipitation for calcium precipitation reaction to obtain a solution after calcium precipitation and gypsum; extracting the calcium-precipitated solution by using P204 to obtain a zinc-removed solution and a refined zinc sulfate solution; and extracting the zinc-removed solution by using P507 to obtain a manganese-removed solution and a refined manganese sulfate solution. According to the method, comprehensive recovery of metal elements in the P204 strip liquor is achieved, resource waste is avoided, and high economic value is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrometallurgy, and in particular relates to a method for comprehensive utilization of P204 stripping solution. Background Art

[0002] In cobalt-nickel hydrometallurgy, the use of P204 extraction is the most important means of impurity removal, that is, after the cobalt-nickel is leached, P204 is used to extract impurities (such as copper, manganese, zinc, calcium, etc.), and after the impurity extraction is completed, sulfuric acid is used to perform stripping to obtain P204 stripping solution. P204 stripping solution mainly contains manganese, copper, zinc, calcium and a small amount of cobalt and nickel, among which manganese content is the highest, and the content of manganese is much greater than the content of copper, and the content of copper is greater than the content of zinc. The current process for treating P204 stripping solution is usually to first adjust the pH of the feed solution to above 4 with alkali solution, and then add copper, cobalt, nickel and zinc in the sodium sulfide precipitation solution, thereby purifying and preparing manganese sulfate solution. However, the existing process does not recycle the sulfides such as copper, cobalt, nickel and zinc generated by precipitation, resulting in waste of resources such as copper sulfide. Summary of the invention

[0003] In order to overcome the above-mentioned defects of the prior art, the object of the present invention is to provide a method for comprehensive utilization of P204 stripping solution to solve the technical problem that the existing process fails to comprehensively recover the valuable metals in the P204 stripping solution.

[0004] To achieve the above object, the present invention is implemented through the following technical solutions: The present application provides a method for comprehensive utilization of P204 stripping solution, comprising the following steps: (1) Deoiling the P204 stripping solution to obtain a deoiled solution; (2) performing an alkali adjustment on the deoiled liquid to obtain an alkali-adjusted liquid; (3) using a primary alkali solution to pickle the crude copper sulfide, and obtaining washed copper sulfide and pickling solution after solid-liquid separation; (4) subjecting the pickling liquid to secondary alkali adjustment, and obtaining secondary alkali adjustment liquid and crude copper hydroxide after solid-liquid separation; (5) adding sulfide to the secondary alkaline adjustment solution to carry out copper precipitation reaction, and obtaining copper precipitation liquid and crude copper sulfide after solid-liquid separation; (6) adding sulfate to the copper precipitation solution to carry out calcium precipitation reaction, and obtaining calcium precipitation solution and gypsum after solid-liquid separation; (7) Extracting the calcium precipitation solution with P204 to obtain zinc removal solution and refined zinc sulfate solution; (8) The zinc-removed liquid is extracted using P507 to obtain manganese-removed liquid and refined manganese sulfate solution.

[0005] Preferably, in step (1), the oil removal process comprises: subjecting the P204 stripping liquid to oil separation or aeration treatment and then allowing it to stand to obtain an oil phase and an aqueous phase; and subjecting the aqueous phase to adsorption treatment using activated carbon to obtain an oil-removed liquid.

[0006] Preferably, in step (2), the deoiled liquid is subjected to a primary alkali adjustment using crude copper hydroxide; in the primary alkali adjustment process, the endpoint pH of the primary alkali adjustment reaction is controlled to be 1.0-1.5.

[0007] Preferably, in step (3), the solid-liquid ratio of pickling is 1:5-6, the pickling time is 3-6 h, and the pickling temperature is 60-70°C.

[0008] Preferably, the above method further comprises the following step: countercurrent washing the washed copper sulfide obtained in step (3) to obtain refined copper sulfide.

[0009] Preferably, the method further comprises the following steps: countercurrent washing the crude copper hydroxide obtained in step (4), and then acid dissolving the copper-poor solution produced by copper electrodeposition to obtain a copper-rich solution.

[0010] Preferably, in step (4), in the secondary alkali adjustment process, the endpoint pH of the secondary alkali adjustment reaction is controlled to be 4.5-5.5; the pickling liquid is subjected to secondary alkali adjustment using alkali solution, and the alkali solution includes one or more of lime milk and sodium hydroxide.

[0011] Preferably, in step (5), the molar ratio of the sulfide to the copper element in the secondary alkaline adjustment solution is (1.5-2.5):1, and the sulfide is one or more of sodium sulfide and ammonium sulfide.

[0012] Preferably, in step (6), the molar ratio of sulfate to calcium in the copper precipitation solution is (2.2-2.5):1; the temperature of the calcium precipitation reaction is 80-95°C, and the reaction time is 1-2h; and the sulfate is one or more of sodium sulfate and ammonium sulfate.

[0013] Preferably, the above method further comprises step (9): recovering the cobalt and nickel in the liquid after manganese removal.

[0014] The beneficial effects of the present invention are: The present invention sequentially performs secondary acid adjustment and copper precipitation reaction on P204 stripping solution, precipitates copper in the solution in two steps, reduces the amount of sulfide used, saves costs, and reduces the generation of copper sulfide tailings. At the same time, the crude copper sulfide tailings are pickled using the P204 stripping solution after the primary acid adjustment, so that the copper sulfide can be refined, thereby effectively recovering the copper in the P204 stripping solution.

[0015] The present invention realizes the recovery of calcium, manganese and zinc in the solution by sequentially performing calcium precipitation, P204 extraction and P507 extraction on the copper-removed solution. In addition, while respectively recovering the impurity elements in the P204 stripping solution, the P204 stripping solution is purified, thereby effectively realizing the recovery of cobalt and nickel, and having high economic value. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solution of the embodiment of the present invention, the drawings of the embodiment are briefly introduced below.

[0017] Figure 1 It is a schematic flow chart of a method for comprehensive utilization of P204 stripping solution of the present invention. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] See also Figure 1 The embodiment of the present invention provides a method for comprehensive utilization of P204 stripping solution, comprising the following steps: (1) Oil removal: The P204 stripping liquid is treated with oil separation or aeration and then left to stand for 24-36 hours to obtain an oil phase and an aqueous phase; the aqueous phase is then adsorbed on activated carbon to obtain an oil-free liquid.

[0020] (2) Primary alkaline adjustment: Use crude copper hydroxide to adjust the pH of the deoiled liquid to 1.0-1.5 to obtain a primary alkaline adjustment solution.

[0021] (3) Pickling: The crude copper sulfide is pickled with a primary alkaline solution, the solid-liquid ratio of the pickling is 1:5-6, the pickling time is 3-6 hours, and the pickling temperature is 60-70°C, to obtain washed copper sulfide and pickling solution. The washed copper sulfide is countercurrently washed to obtain refined copper sulfide. Preferably, the countercurrent washing water-solid-liquid ratio is 1:1-2, the washing time is 1-2 hours, and the washing temperature is 60-80°C. The refined copper sulfide contains 15-25% copper, 35-45% water, less than 0.15% nickel, cobalt, manganese and zinc, and less than 0.15% chloride ions.

[0022] (4) Secondary alkali adjustment: Use alkali solution to adjust the pH of the pickling solution to 4.5-5.5, obtain secondary alkali adjustment solution and crude copper hydroxide after solid-liquid separation, and perform countercurrent washing on the crude copper hydroxide. Preferably, the countercurrent washing water-solid-liquid ratio is 1:1-2, the washing time is 1-2h, and the washing temperature is 60-80°C. The alkali solution is preferably one or more of 20-30% lime milk and 25-35% sodium hydroxide. Then, the washed crude copper hydroxide is acid-dissolved using the copper-poor solution generated by copper electrodeposition to obtain a copper-rich solution. The copper-poor solution contains 28-30g / L copper and 2.0-2.2mol / L hydrogen ions; the copper-rich solution contains 40-45g / L copper and 1.5-1.6mol / L hydrogen ions.

[0023] (5) Copper precipitation: sulfide is added to the secondary alkaline solution to carry out copper precipitation reaction, and after solid-liquid separation, a copper precipitation solution and crude copper sulfide are obtained; the molar ratio of sulfide to copper element in the secondary alkaline solution is (1.5-2.5):1, and the sulfide is one or more of sodium sulfide and ammonium sulfide. The crude copper sulfide contains 5-15% copper, 0.1-1.5% nickel, 0.5-3% cobalt, 4-9% manganese, 2-5% zinc, 1-1.5% chloride ion, and 35-50% water.

[0024] (6) Calcium precipitation: Sulfate is added to the copper precipitation solution to carry out calcium precipitation reaction, and the calcium precipitation solution and gypsum are obtained after solid-liquid separation; the molar ratio of sulfate to calcium element in the copper precipitation solution is (2.2~2.5):1; the temperature of the calcium precipitation reaction is 80-95℃, and the reaction time is 1-2h; the sulfate is one or more of sodium sulfate and ammonium sulfate. The calcium content in the calcium precipitation solution is 600-800mg / L.

[0025] (7) P204 extraction: The decalcified liquid is extracted with P204 to obtain the dezincified liquid and refined zinc sulfate solution.

[0026] (8) P507 extraction: The zinc-removed liquid is extracted with P507 to obtain manganese-removed liquid and refined manganese sulfate solution.

[0027] (9) Recovery of cobalt and nickel: The liquid after manganese removal is subjected to precipitation enrichment and resin adsorption to obtain a cobalt-nickel enriched product.

[0028] In order to make the objectives, technical solutions and advantages of the present invention more clear, the embodiments of the present invention will be described in further detail below.

[0029] In the following examples, the P204 stripping solution contains 5-15 g / L copper, 0.1-0.5 g / L nickel, 0.5-1.5 g / L cobalt, 60-80 g / L manganese, 8-12 g / L calcium, 0.1-0.5 g / L magnesium, 5-15 g / L zinc, 0.1-0.12 mol / L hydrogen ions, and 195-230 g / L chloride ions.

[0030] Example 1 A method for comprehensive utilization of P204 stripping solution comprises the following steps: (1) Oil removal: After the P204 stripping liquid passes through the oil separator, it is left to stand for 24 hours to obtain an oil phase and an aqueous phase; then the aqueous phase is passed through an activated carbon column to obtain the deoiled liquid.

[0031] (2) Primary alkaline adjustment: Use crude copper hydroxide to adjust the pH of the deoiled liquid to 1.0 to obtain a primary alkaline adjustment solution.

[0032] (3) Pickling: Take an appropriate amount of crude copper sulfide, slurry it with primary alkali, the solid-liquid ratio is 1:5, pickle it at 60℃ for 3h, and obtain pickled copper sulfide tailings and pickling liquid. The pickled copper sulfide tailings are subjected to two-stage countercurrent washing to obtain refined copper sulfide. The countercurrent washing water-solid-liquid ratio is 1:2, the washing time is 1h, and the washing temperature is 60℃. The refined copper sulfide contains 15% copper, 35% water, 0.1% nickel, cobalt, manganese and zinc, and 0.11% chloride ions.

[0033] (4) Secondary alkaline adjustment: Use 30% lime milk to adjust the pH of the pickling solution to 4.5, and obtain a secondary alkaline adjustment solution and crude copper hydroxide after solid-liquid separation. Take part of the crude copper hydroxide for primary alkaline adjustment in step (2), and perform two-stage countercurrent washing on the remaining crude copper hydroxide. The countercurrent washing water-to-solid ratio is 1:2, the washing time is 1h, and the washing temperature is 60°C. Then, the washed crude copper hydroxide is acid-dissolved with the copper-poor solution generated by copper electrodeposition to obtain a copper-rich solution. The copper-poor solution contains 28g / L copper and 2.0mol / L hydrogen ions; the copper-rich solution contains 40g / L copper and 1.5mol / L hydrogen ions.

[0034] (5) Copper precipitation: Sodium sulfide is added to the secondary alkaline solution to carry out copper precipitation reaction, and the molar ratio of sodium sulfide to copper element in the secondary alkaline solution is 1.5:1. After solid-liquid separation, a copper precipitation liquid and crude copper sulfide are obtained, and the crude copper sulfide is returned to step (3) to prepare refined copper sulfide. The crude copper sulfide contains 5% copper, 0.1% nickel, 0.5% cobalt, 4% manganese, 2% zinc, 1% chloride ion, and 35% water.

[0035] (6) Calcium precipitation: anhydrous sodium sulfate is added to the copper precipitation liquid to carry out calcium precipitation reaction, and the calcium precipitation liquid and gypsum are obtained after solid-liquid separation; the molar ratio of anhydrous sodium sulfate to calcium in the copper precipitation liquid is 2.2:1; the temperature of the calcium precipitation reaction is 80°C, and the reaction time is 1h. The calcium content in the calcium precipitation liquid is 800mg / L.

[0036] (7) P204 extraction: P204 is used to extract the post-calcification liquid to obtain a post-zinc removal liquid and a refined zinc sulfate solution. Specifically, P204 is mixed with sulfonated kerosene to obtain an extracted organic phase with a dilution rate of 20%; the extracted organic phase is mixed with the post-calcification liquid at a volume ratio of 1:0.4 to extract zinc, and the extraction level is 8 to obtain a loaded organic phase and a raffinate, i.e., the post-zinc removal liquid; 0.25 mol / L sulfuric acid solution is used to wash the loaded organic phase at a volume ratio of 1:20, and the washing level is 6 to obtain a zinc-rich organic phase and washing water. The zinc-rich organic phase is mixed with a sulfuric acid solution with a concentration of 2.0 mol / L at a volume ratio of 20:1, and stripping is performed, and the stripping level is 7 to obtain a refined zinc sulfate solution. The refined zinc sulfate solution contains 160 mg / L zinc, 1.5 mg / L calcium, 1.2 mg / L cobalt, 0.5 mg / L nickel, 0.5 mg / L copper and 0.1 mol / L hydrogen ion.

[0037] (8) P507 extraction: P507 is used to extract the zinc removal liquid to obtain a manganese removal liquid and a refined manganese sulfate solution. Specifically, P507 is mixed with sulfonated kerosene to obtain an extracted organic phase with a dilution rate of 20%; the extracted organic phase is mixed with the zinc removal liquid at a volume ratio of 1:0.4 to extract manganese, the extraction level is 8, and a loaded organic phase and a raffinate, i.e., the manganese removal liquid, are obtained; 0.25 mol / L sulfuric acid solution is used to wash the loaded organic phase at a volume ratio of 1:20, the washing level is 6, and a manganese-rich organic phase and washing water are obtained. The manganese-rich organic phase is mixed with a 2.0 mol / L sulfuric acid solution at a volume ratio of 20:1, and stripping is performed, the stripping level is 7, and a refined manganese sulfate solution is obtained. The refined manganese sulfate solution contains 165 g / L manganese, 1.5 mg / L calcium, and 0.1 mg / L copper.

[0038] (9) Recovery of cobalt and nickel: Add precipitant liquid alkali to the manganese removal solution to reduce the cobalt and nickel in the solution to 5-10 mg / L, obtain a cobalt-nickel enriched product and a precipitated solution, and return the obtained cobalt-nickel enriched product to the cobalt-nickel leaching process. Pass the precipitated solution through a D352 resin column to reduce the cobalt and nickel in the solution to 0.1 mg / L, then regenerate the resin with 0.5-2 mol / L sulfuric acid, and use the regenerated solution as bottom water in the cobalt-nickel leaching process.

[0039] Example 2 A method for comprehensive utilization of P204 stripping solution comprises the following steps: (1) Oil removal: After the P204 stripping liquid passes through the oil separator, it is left to stand for 24 hours to obtain an oil phase and an aqueous phase; then the aqueous phase is passed through an activated carbon column to obtain the deoiled liquid.

[0040] (2) Primary alkaline adjustment: Use crude copper hydroxide to adjust the pH of the deoiled liquid to 1.5 to obtain a primary alkaline adjustment solution.

[0041] (3) Pickling: Take an appropriate amount of crude copper sulfide, slurry it with primary alkali, solid-liquid ratio of 1:5, pickle at 65℃ for 4h, and obtain pickled copper sulfide tailings and pickling liquid. The pickled copper sulfide tailings are subjected to two-stage countercurrent washing to obtain refined copper sulfide. The countercurrent washing water-solid-liquid ratio is 1:2, the washing time is 1h, and the washing temperature is 60℃. The refined copper sulfide contains 20% copper, 40% water, 0.08% nickel, cobalt, manganese and zinc, and 0.06% chloride ion.

[0042] (4) Secondary alkaline adjustment: Use 25% lime milk to adjust the pH of the pickling solution to 5.0, and obtain a secondary alkaline adjustment solution and crude copper hydroxide after solid-liquid separation. Take part of the crude copper hydroxide for primary alkaline adjustment in step (2), and perform two-stage countercurrent washing on the remaining crude copper hydroxide. The countercurrent washing solid-liquid ratio is 1:2, the washing time is 1h, and the washing temperature is 60°C. Then, the washed crude copper hydroxide is acid-dissolved with the copper-poor solution generated by copper electrodeposition to obtain a copper-rich solution. The copper-poor solution contains 28g / L copper and 2.0mol / L hydrogen ions; the copper-rich solution contains 42g / L copper and 1.55mol / L hydrogen ions.

[0043] (5) Copper precipitation: Sodium sulfide is added to the secondary alkaline solution to carry out copper precipitation reaction, and the molar ratio of sodium sulfide to copper element in the secondary alkaline solution is 2:1. After solid-liquid separation, a copper precipitation liquid and crude copper sulfide are obtained, and the crude copper sulfide is returned to step (3) to prepare refined copper sulfide. The crude copper sulfide contains 10% copper, 1.0% nickel, 2% cobalt, 5% manganese, 4% zinc, 1.2% chloride ions, and 40% water.

[0044] (6) Calcium precipitation: anhydrous sodium sulfate is added to the copper precipitation liquid to carry out calcium precipitation reaction, and the calcium precipitation liquid and gypsum are obtained after solid-liquid separation; the molar ratio of anhydrous sodium sulfate to calcium in the copper precipitation liquid is 2.4:1; the temperature of the calcium precipitation reaction is 85°C, and the reaction time is 1h. The calcium content in the calcium precipitation liquid is 700mg / L.

[0045] (7) P204 extraction: P204 is used to extract the post-calcification liquid to obtain a zinc-free liquid and a refined zinc sulfate solution. P204 is mixed with sulfonated kerosene to obtain an extracted organic phase with a dilution rate of 30%; the extracted organic phase is mixed with the post-calcification liquid at a volume ratio of 1:0.3 to extract zinc, with the extraction stage being 9, to obtain a loaded organic phase and a raffinate; 1 mol / L sulfuric acid solution is used to wash the loaded organic phase at a volume ratio of 1:20, with the washing stage being 9, to obtain a zinc-rich organic phase and washing water. The zinc-rich organic phase is mixed with a 2.0 mol / L sulfuric acid solution at a volume ratio of 15:1, and stripping is performed, with the stripping stage being 8, to obtain a refined zinc sulfate solution. The refined zinc sulfate solution contains 170 mg / L zinc, 0.8 mg / L calcium, 0.6 mg / L cobalt, 0.8 mg / L nickel, 0.3 mg / L copper and 0.15 mol / L hydrogen ion.

[0046] (8) P507 extraction: P507 is used to extract the zinc removal liquid to obtain manganese removal liquid and refined manganese sulfate solution. Specifically, P507 is mixed with sulfonated kerosene to obtain an extracted organic phase with a dilution rate of 30%; the extracted organic phase is mixed with the zinc removal liquid at a volume ratio of 1:0.1 to extract manganese, the extraction level is 9, and a loaded organic phase and a raffinate are obtained; 0.5 mol / L sulfuric acid solution is used to wash the loaded organic phase at a volume ratio of 1:20, the washing level is 6, and a manganese-rich organic phase and washing water are obtained. The manganese-rich organic phase is mixed with a sulfuric acid solution with a concentration of 2.5 mol / L at a volume ratio of 10:1, and stripping is performed, the stripping level is 8, and a refined manganese sulfate solution is obtained. The refined manganese sulfate solution contains 185 g / L manganese, 0.8 mg / L calcium, and 0.1 mg / L copper.

[0047] (9) Recovery of cobalt and nickel: Add sodium sulfide as a precipitant to the manganese removal solution to reduce the cobalt and nickel in the solution to 5-10 mg / L, obtain a cobalt-nickel enriched product and a precipitated solution, and return the obtained cobalt-nickel enriched product to the cobalt-nickel leaching process. Pass the precipitated solution through a D351 resin column to reduce the cobalt and nickel in the solution to 0.1 mg / L, then regenerate the resin with 0.5-2 mol / L sulfuric acid, and use the regenerated solution as bottom water in the cobalt-nickel leaching process.

[0048] Example 3 A method for comprehensive utilization of P204 stripping solution comprises the following steps: (1) Oil removal: After the P204 stripping liquid passes through the oil separator, it is left to stand for 24 hours to obtain an oil phase and an aqueous phase; then the aqueous phase is passed through an activated carbon column to obtain the deoiled liquid.

[0049] (2) Primary alkaline adjustment: Use crude copper hydroxide to adjust the pH of the deoiled liquid to 1.5 to obtain a primary alkaline adjustment solution.

[0050] (3) Pickling: Take an appropriate amount of crude copper sulfide, slurry it with primary alkali, the solid-liquid ratio is 1:5, pickle it at 70℃ for 4h, and obtain pickled copper sulfide tailings and pickling liquid. The pickled copper sulfide tailings are subjected to two-stage countercurrent washing to obtain refined copper sulfide. The countercurrent washing water-solid-liquid ratio is 1:2, the washing time is 1h, and the washing temperature is 60℃. The refined copper sulfide contains 25% copper, 45% water, 0.05% nickel, cobalt, manganese and zinc, and 0.06% chloride ion.

[0051] (4) Secondary alkaline adjustment: Use 25% lime milk to adjust the pH of the pickling solution to 5.5, and obtain a secondary alkaline adjustment solution and crude copper hydroxide after solid-liquid separation. Take part of the crude copper hydroxide for primary alkaline adjustment in step (2), and perform two-stage countercurrent washing on the remaining crude copper hydroxide. The countercurrent washing water-solid-liquid ratio is 1:2, the washing time is 1h, and the washing temperature is 60°C. Then, the washed crude copper hydroxide is acid-dissolved with the copper-poor solution generated by copper electrodeposition to obtain a copper-rich solution. The copper-poor solution contains 28g / L copper and 2.0mol / L hydrogen ions; the copper-rich solution contains 45g / L copper and 1.6mol / L hydrogen ions.

[0052] (5) Copper precipitation: Sodium sulfide is added to the secondary alkaline solution to carry out copper precipitation reaction, and the molar ratio of sodium sulfide to copper element in the secondary alkaline solution is 2.5:1. After solid-liquid separation, a copper precipitation liquid and crude copper sulfide are obtained, and the crude copper sulfide is returned to step (3) to prepare refined copper sulfide. The crude copper sulfide contains 15% copper, 1.5% nickel, 3% cobalt, 9% manganese, 5% zinc, 1.5% chloride ions, and 50% water.

[0053] (6) Calcium precipitation: anhydrous sodium sulfate is added to the copper precipitation liquid to carry out calcium precipitation reaction, and the calcium precipitation liquid and gypsum are obtained after solid-liquid separation; the molar ratio of anhydrous sodium sulfate to calcium in the copper precipitation liquid is 2.5:1; the temperature of the calcium precipitation reaction is 95°C, and the reaction time is 1h. The calcium content in the calcium precipitation liquid is 600mg / L.

[0054] (7) P204 extraction: P204 is used to extract the post-calcification liquid to obtain a zinc-free liquid and a refined zinc sulfate solution. P204 is mixed with sulfonated kerosene to obtain an extracted organic phase with a dilution rate of 20%; the extracted organic phase is mixed with the post-calcification liquid at a volume ratio of 1:0.1 to extract zinc, with the extraction level of 7, to obtain a loaded organic phase and a raffinate; 0.25 mol / L sulfuric acid solution is used to wash the loaded organic phase at a volume ratio of 1:10, with the washing level of 6, to obtain a zinc-rich organic phase and washing water. The zinc-rich organic phase is mixed with a 2.5 mol / L sulfuric acid solution at a volume ratio of 10:1, and stripping is performed, with the stripping level of 9, to obtain a refined zinc sulfate solution. The refined zinc sulfate solution contains 150 mg / L zinc, 0.1 mg / L calcium, 0.1 mg / L cobalt, 0.15 mg / L nickel, 0.1 mg / L copper and 0.1 mol / L hydrogen ion.

[0055] (8) P507 extraction: P507 is used to extract the zinc removal liquid to obtain manganese removal liquid and refined manganese sulfate solution. Specifically, P507 is mixed with sulfonated kerosene to obtain an extracted organic phase with a dilution rate of 25%; the extracted organic phase is mixed with the zinc removal liquid at a volume ratio of 1:0.2 to extract manganese, the extraction level is 7, and a loaded organic phase and a raffinate are obtained; 0.25 mol / L sulfuric acid solution is used to wash the loaded organic phase at a volume ratio of 1:20, the washing level is 6, and a manganese-rich organic phase and washing water are obtained. The manganese-rich organic phase is mixed with a 2.0 mol / L sulfuric acid solution at a volume ratio of 20:1, and stripping is performed, the stripping level is 9, and a refined manganese sulfate solution is obtained. The refined manganese sulfate solution contains 155 g / L manganese, 0.1 mg / L calcium, and 0.1 mg / L copper.

[0056] (9) Recovery of cobalt and nickel: Add precipitant liquid alkali to the manganese removal solution to reduce the cobalt and nickel in the solution to 5-10 mg / L, obtain a cobalt-nickel enriched product and a precipitated solution, and return the obtained cobalt-nickel enriched product to the cobalt-nickel leaching process. Pass the precipitated solution through a D351 resin column to reduce the cobalt and nickel in the solution to 0.1 mg / L, then regenerate the resin with 0.5-2 mol / L sulfuric acid, and use the regenerated solution as bottom water in the cobalt-nickel leaching process.

[0057] In summary, the present application sequentially removes oil from P204, performs an alkali adjustment once, and uses an alkali adjustment liquid to acid-wash the crude copper sulfide obtained by the copper precipitation reaction; then performs a secondary alkali adjustment and copper precipitation, and realizes the recovery of copper in the solution through a two-step reaction. Finally, the solution after copper precipitation is subjected to calcium precipitation and extraction treatment, and calcium, manganese and zinc therein are recovered respectively, and the cobalt and nickel in the solution after manganese removal are reused, thereby realizing the comprehensive recovery and utilization of metal elements in the P204 stripping solution, avoiding waste of resources, and having high economic value.

[0058] It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own focus. For matters that are not described in detail in some embodiments, reference may be made to the description in other embodiments.

[0059] The above-mentioned embodiments only express the implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for comprehensive utilization of P204 stripping solution, characterized in that: The following steps are involved: (1) Deoiling the P204 stripping solution to obtain a deoiled solution; (2) performing an alkali adjustment on the deoiled liquid to obtain an alkali-adjusted liquid; (3) using the primary alkali adjustment solution to acid wash the crude copper sulfide, and obtaining washed copper sulfide and acid washing solution after solid-liquid separation; (4) subjecting the pickling solution to secondary alkali adjustment, and obtaining a secondary alkali adjustment solution and crude copper hydroxide after solid-liquid separation; (5) adding sulfide to the secondary alkaline solution to carry out copper precipitation reaction, and obtaining copper precipitation liquid and crude copper sulfide after solid-liquid separation; (6) adding sulfate to the copper precipitation liquid to carry out calcium precipitation reaction, and obtaining calcium precipitation liquid and gypsum after solid-liquid separation; (7) extracting the calcium precipitation solution with P204 to obtain zinc removal solution and refined zinc sulfate solution; (8) The zinc-removed liquid is extracted using P507 to obtain a manganese-removed liquid and a refined manganese sulfate solution.

2. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: In step (1), the oil removal process comprises: subjecting the P204 stripping liquid to oil separation or aeration treatment and then allowing it to stand to obtain an oil phase and an aqueous phase; and subjecting the aqueous phase to adsorption treatment using activated carbon to obtain an oil-removed liquid.

3. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: In step (2), the deoiled liquid is subjected to a primary alkali adjustment using crude copper hydroxide; in the primary alkali adjustment process, the endpoint pH of the primary alkali adjustment reaction is controlled to be 1.0-1.

5.

4. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: In step (3), the solid-liquid ratio of the pickling is 1:5-6, the pickling time is 3-6 h, and the pickling temperature is 60-70°C.

5. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: The method further comprises the following step: countercurrent washing the washed copper sulfide obtained in step (3) to obtain refined copper sulfide.

6. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: The method further comprises the following steps: countercurrent washing the crude copper hydroxide obtained in step (4), and then acid dissolving the copper-poor solution produced by copper electrodeposition to obtain a copper-rich solution.

7. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: In step (4), in the secondary alkali adjustment process, the endpoint pH of the secondary alkali adjustment reaction is controlled to be 4.5-5.5; the pickling liquid is subjected to secondary alkali adjustment using alkali solution, and the alkali solution includes one or more of lime milk and sodium hydroxide.

8. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: In step (5), the molar ratio of the sulfide to the copper element in the secondary alkaline adjustment solution is (1.5-2.5):1, and the sulfide is one or more of sodium sulfide and ammonium sulfide.

9. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: In step (6), the molar ratio of the sulfate to the calcium element in the copper precipitation solution is (2.2-2.5):1; the temperature of the calcium precipitation reaction is 80-95°C, and the reaction time is 1-2h; the sulfate is one or more of sodium sulfate and ammonium sulfate.

10. The method for comprehensive utilization of P204 stripping solution according to claim 1, characterized in that: The method also includes step (9): recovering the cobalt and nickel in the liquid after manganese removal.

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