Process for the preparation of hydroxides from antifouling paints

Abstract

The present application relates to the technical field of hydrometallurgy, and discloses a method for preparing hydroxide from reverse copper-manganese solution, which comprises the following steps: controlling the potential of the reverse copper-manganese solution to carry out sulfidation copper deposition, so as to obtain a copper deposition solution; adjusting the pH of the copper deposition solution to 4-6, mixing the copper deposition solution with manganese powder to carry out manganese-zinc replacement, and obtaining zinc-manganese slag and a zinc deposition solution after sufficient reaction; mixing the zinc-manganese slag with sufficient zinc-dissolving alkali solution to carry out reaction, and obtaining manganese slag and the zinc-dissolving solution after solid-liquid separation; adjusting the pH of the zinc-dissolving solution to 7-8, and carrying out solid-liquid separation after sufficient reaction, so as to obtain zinc hydroxide. The method has a short overall process, good separation and purification effect, and can obtain crude manganese hydroxide and zinc hydroxide products.

Description

Technical Field

[0001] This invention relates to the field of hydrometallurgical technology, and more specifically, to a method for preparing hydroxides from anti-copper-manganese liquid. Background Technology

[0002] In the hydrometallurgical process of cobalt, P2O4 is used to selectively extract impurities such as copper, manganese, and zinc from the cobalt-containing solution. The resulting solution is a strongly acidic solution rich in copper, manganese, and zinc, which is called the copper-manganese solution.

[0003] Typically, copper-manganese solutions contain 1–2 g / L of copper, as high as 70–80 g / L of manganese, and 5–10 g / L of zinc. They also contain 0.01–3 g / L of calcium, cobalt, and magnesium, which have high recovery value but are difficult to process. Some companies use direct precipitation to treat copper-manganese solutions. While this method is simple and low-cost, the similar precipitation pH of these metals makes direct precipitation difficult to separate and purify them, thus failing to fully utilize their potential value.

[0004] From the perspective of resource recycling and environmental protection, some companies currently use extractants to separate and purify basic zinc carbonate and battery-grade manganese sulfate. However, since the market value of these two products is far lower than that of metals such as cobalt, nickel, and copper, the extraction process results in the consumption of large amounts of extractants, acids, alkalis, resins, activated carbon, and other auxiliary materials. Furthermore, the process is lengthy, leading to high material losses, energy consumption, and labor costs, as well as demanding equipment requirements. These factors mean that the cost of treating copper-manganese solutions through extraction covers the intrinsic value of the produced products.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The object of the present invention is to provide a method for preparing hydroxides from anti-copper-manganese solution, which aims to improve at least one of the problems mentioned in the background art.

[0007] This invention is implemented as follows:

[0008] In a first aspect, the present invention provides a method for preparing hydroxides using an anti-copper-manganese solution, comprising:

[0009] Sulfide copper precipitation: The potential of the anti-copper manganese solution is controlled to carry out sulfide copper precipitation, and the copper precipitation solution is obtained.

[0010] Zinc precipitation: Adjust the pH of the copper precipitation solution to 4-6, mix the copper precipitation solution with manganese powder, perform manganese-zinc replacement, and after full reaction, obtain zinc-manganese slag and zinc precipitation solution;

[0011] Crude zinc hydroxide: Zinc-manganese slag is mixed with sufficient alkaline solution and reacted. After solid-liquid separation, manganese slag and zinc-dissolving liquid are obtained. The pH of the zinc-dissolving liquid is adjusted to 7-8. After sufficient reaction, solid-liquid separation is performed to obtain zinc hydroxide.

[0012] In an optional embodiment, the preparation method further includes a manganese powder reuse step: washing the manganese slag to obtain recycled manganese powder, which can be directly reused in the zinc precipitation step.

[0013] In an optional embodiment, a deep zinc precipitation step is included after the zinc precipitation step: the pH of the zinc precipitation solution is maintained within 4 to 6, manganese sulfide is added to the zinc precipitation solution, and after the zinc ions react fully with the manganese sulfide, a manganese sulfide slag and a deep zinc precipitation solution are obtained.

[0014] In an optional embodiment, the replaced manganese sulfide slag is sufficient to be reused in the deep zinc precipitation step, where it reacts fully with the residual zinc ions in the zinc precipitation solution. Therefore, the replaced manganese sulfide slag is then reused as manganese sulfide that reacts with zinc ions.

[0015] In an optional embodiment, the deep zinc precipitation step is followed by a manganese precipitation step: a manganese precipitation alkaline solution is added to the liquid after deep zinc precipitation, and the pH at the reaction endpoint is controlled to be 9.0 to 9.5. After the reaction is complete, solid-liquid separation is performed to obtain crude manganese hydroxide.

[0016] In an optional embodiment, the sum of the amount of manganese powder added during zinc precipitation and the amount of manganese sulfide added during deep zinc precipitation is 1.5 to 5.0 times the zinc ion equivalent in the anti-copper manganese solution.

[0017] In an optional embodiment, the amount of manganese powder added is 1.0 to 2.0 times the zinc ion equivalent in the anti-copper manganese solution.

[0018] In an optional embodiment, the amount of manganese sulfide added is 0.4 to 0.6 times the zinc ion equivalent in the anti-copper manganese solution.

[0019] In an optional implementation, the replacement manganese sulfide slag is reused 5 to 10 times.

[0020] In an optional embodiment, during the zinc immersion process, the copper immersion liquid is mixed with manganese powder and stirred at 300-400 r / min for 0.5-1.5 h.

[0021] In an optional implementation, during the manganese precipitation process, manganese sulfide is added dropwise to the zinc precipitation solution using a slurry-like method.

[0022] In an optional embodiment, during the deep zinc immersion process, the addition of manganese sulfide to the zinc immersion liquid is carried out under stirring at a speed of 300-400 r / min. After the manganese sulfide is added, the stirring reaction continues for 0.5-1.5 h.

[0023] In an optional embodiment, the manganese precipitation alkaline solution used in the manganese precipitation process is a sodium hydroxide solution; optionally, the reaction continues for 30 to 90 minutes after the manganese precipitation alkaline solution is added dropwise.

[0024] In an optional embodiment, the zinc-dissolving alkaline solution used in the preparation of crude zinc hydroxide is a sodium hydroxide solution, ammonia water, or a mixture of the two.

[0025] In an optional embodiment, the mass ratio of zinc-manganese slag to zinc alkali solution is 1:1 to 20.

[0026] In an optional embodiment, the mass ratio of zinc-manganese slag to zinc alkali solution is 1:7 to 10.

[0027] In an optional embodiment, the substance used to wash the manganese slag is water or a dilute acid solution.

[0028] In an optional implementation, copper sulfide plating specifically involves:

[0029] Under a stirring rate of 300–400 r / min, sodium hydroxide solution is added dropwise to adjust the pH of the copper-manganese solution to the range of 1.0–1.2. Then, sodium sulfide solution is added dropwise. When the potential drops to 0–50 mV, the addition is stopped, and stirring is continued for 25–35 min. During the stirring process, Na2S solution is added dropwise to control the potential to maintain 0–50 mV. After stirring is completed, solid-liquid separation is performed to obtain copper slag and copper-precipitated liquid.

[0030] Optionally, the molar concentration of the added sodium sulfide solution is 0.5–1.5 mol / L.

[0031] The present invention has the following beneficial effects:

[0032] The method provided in this invention involves copper precipitation followed by zinc precipitation. Because the solubility product of copper sulfide precipitate is much smaller than that of zinc sulfide and manganese sulfide, the potential control range is large, eliminating the need for precise control during copper precipitation. The overall process is also more concise. Using manganese powder for the displacement reaction results in a rapid and efficient reaction without introducing other impurities or consuming additional auxiliary materials, thus reducing costs. Sufficient manganese powder can treat copper-manganese solutions with high zinc content. After the zinc precipitation step, alkaline leaching of the zinc-manganese slag, followed by adjusting the pH of the leaching solution (post-zinc precipitation solution) to 7-8, yields zinc hydroxide, enabling resource recycling. Attached Figure Description

[0033] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 A flowchart of the preparation method provided in an embodiment of the present invention. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Specific examples will be used to illustrate the technical solutions of the present invention. Those skilled in the art should understand that the embodiments are merely illustrative of the present invention and should not be considered as specific limitations on the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0036] The method for preparing hydroxides using anticopper-manganese solution provided in the embodiments of the present invention will be described in detail below.

[0037] This invention provides a method for preparing hydroxides using an anti-copper-manganese solution, comprising:

[0038] Sulfide copper precipitation: The potential of the anti-copper manganese solution is controlled to carry out sulfide copper precipitation, and the copper precipitation solution is obtained.

[0039] Zinc precipitation: Adjust the pH of the copper precipitation solution to 4-6, mix the copper precipitation solution with manganese powder, perform manganese-zinc replacement, and after full reaction, obtain zinc-manganese slag and zinc precipitation solution;

[0040] Crude zinc hydroxide: Zinc-manganese slag is mixed with a sufficient amount of zinc-dissolving alkaline solution and reacted. After solid-liquid separation, manganese slag and zinc-dissolving liquid are obtained. The pH of the zinc-dissolving liquid is adjusted to 7-8, and after sufficient reaction, solid-liquid separation is performed to obtain zinc hydroxide.

[0041] The preparation method provided by this invention has the following advantages:

[0042] The method provided in this invention involves copper precipitation followed by zinc precipitation. Because the solubility product of copper sulfide precipitate is much smaller than that of zinc sulfide and manganese sulfide, the potential control range is large, eliminating the need for precise control during copper precipitation. The overall process is also more concise. Using manganese powder for the displacement reaction results in a rapid and efficient reaction without introducing other impurities or consuming additional auxiliary materials, thus reducing costs. Sufficient manganese powder can treat copper-manganese solutions with high zinc content. After the zinc precipitation step, alkaline leaching of the zinc-manganese slag, followed by adjusting the pH of the leaching solution (post-zinc precipitation solution) to 7-8, yields zinc hydroxide, enabling resource recycling.

[0043] like Figure 1 As shown, specifically, the preparation method is as follows:

[0044] S1, Activated Carbon Degreasing

[0045] Activated carbon is added to the anti-copper-manganese solution to allow it to fully adsorb the oil. After filtration, the de-oiled solution is obtained.

[0046] S2, copper sulfide plating

[0047] Under a stirring rate of 300-400 r / min, sodium hydroxide solution is added dropwise to adjust the pH of the degreased liquid to the range of 1.0-1.2. Then, sodium sulfide solution is added dropwise. When the potential drops to 0-50 mV, the addition is stopped and stirring is continued for 25-35 min. During the stirring process, Na2S solution is added dropwise to control the potential to maintain 0-50 mV. After stirring is completed, solid-liquid separation is performed to obtain copper slag (copper sulfide coarse slag) and copper slag liquid.

[0048] The resulting copper sulfide slag can be returned to the leaching workshop.

[0049] In this step, taking advantage of the fact that the solubility product of copper sulfide precipitate is much smaller than that of zinc sulfide and manganese sulfide, sodium sulfide is added dropwise under controlled potential, and Cu can be selectively separated first. The reaction equations are (1)-(3).

[0050] Cu+S 2- → CuS (s) k sp = 1.3 × 10 -36 (1)

[0051] Zn+S 2- → ZnS (s) k sp = 1.6 × 10 -24 (2)

[0052] Mn+S 2- → MnS (s) k sp = 1.6 × 10 -14 (3).

[0053] S3, Zinc immersion (first stage of zinc immersion)

[0054] Adjust the pH of the copper precipitation solution to 4–6 (e.g., 4, 4.5, 5, 5.5 or 6), mix the copper precipitation solution with manganese powder, perform manganese-zinc replacement, and after full reaction, obtain zinc-manganese slag and zinc precipitation solution.

[0055] In this step, manganese powder is used to remove zinc from the solution by displacement. The reaction principle is shown in equation (4):

[0056] Zn 2+ (q)+Mn (s) → Zn (s) + Mn 2+ (q) (4).

[0057] Optionally, in order to ensure that the copper plating solution and manganese powder can be fully and quickly mixed and reacted, the copper plating solution and manganese powder are mixed and stirred at 300-400 r / min for 0.5-1.5 h (e.g. 0.5 h, 1 h or 1.5 h), and 1 h is generally selected.

[0058] Optionally, to ensure more thorough and efficient zinc precipitation, the pH of the copper precipitation solution is adjusted to 5.0–5.5 (e.g., 5.0) before being mixed with manganese powder.

[0059] Optionally, the total amount of manganese powder added and the amount of manganese sulfide added during the subsequent deep zinc precipitation process is 1.5 to 5.0 times (e.g., 1.5, 2, 3, 4, or 5 times) the zinc ion equivalent in the copper-manganese solution to ensure that zinc is fully separated from the copper-manganese solution; more preferably, in this step, the amount of manganese powder added is 1.0 to 2.0 times (e.g., 1.5, 2, or 2.5 times) the zinc ion equivalent in the copper-manganese solution; even more preferably, the amount of manganese powder added is 2 times the zinc ion equivalent in the copper-manganese solution.

[0060] This step uses manganese powder to precipitate zinc, which has a fast reaction speed and can remove most of the zinc from the copper-manganese solution.

[0061] S4, Deep Zinc Immersion (Two-Stage Zinc Immersion)

[0062] Maintain the pH of the zinc precipitation solution within the range of 4 to 6 (e.g., 4, 4.5, 5, 5.5, or 6), add manganese sulfide to the zinc precipitation solution, and after the zinc ions react fully with the manganese sulfide, obtain the manganese sulfide slag and the deep zinc precipitation solution after deep zinc precipitation.

[0063] In this step, the reaction principle of deep zinc precipitation using manganese sulfide is as shown in equation (5):

[0064] MnS(s) + Zn 2+ (q) → ZnS (s) + Mn 2+ (q) (5).

[0065] Optionally, to enable manganese sulfide to disperse more quickly in the zinc precipitation solution, manganese sulfide is added dropwise to the zinc precipitation solution using a solid-liquid ratio of 1:2.5 to 3.5 (e.g., 1:2.5, 1:3, or 1:3.5). That is, manganese sulfide is slurried at a solid-liquid ratio of 1:2.5 to 3.5 to obtain a manganese sulfide slurry, which is then added dropwise to the zinc precipitation solution.

[0066] Optionally, in order to ensure that manganese sulfide can fully react with zinc in the zinc precipitation solution, in this step, after adding manganese sulfide to the zinc precipitation solution, the reaction is continuously stirred for 0.5 to 1.5 hours (e.g., 0.5 hours, 1 hour, or 1.5 hours); optionally, the reaction time is 1 hour.

[0067] Optionally, to ensure more complete and efficient zinc precipitation, manganese sulfide is added to the solution after zinc precipitation when the pH is adjusted to 5.0–5.5 (e.g., 5.0, 5.2, or 5.5).

[0068] Optionally, after the zinc precipitation process has removed most of the zinc from the copper-manganese solution, since the amount of zinc ions remaining in the post-precipitation solution is trace, it is not necessary to add too much manganese sulfide in this step. However, to ensure sufficient zinc separation, the amount of manganese sulfide added is 0.4–0.6 (e.g., 0.4, 0.5, or 0.6) times the zinc ion equivalent in the copper-manganese solution. In this step, because the amount of manganese sulfide added is relatively high, it can be reused 5–10 times for further zinc precipitation.

[0069] By combining the deep zinc precipitation step with the zinc precipitation step, this method achieves a separation and purification effect comparable to that of extraction methods, without introducing other impurities. A two-stage process combining manganese powder and manganese sulfide is employed to achieve deep zinc precipitation, solving the problems of the manganese powder replacement process being fast but insufficient in depth, and the manganese sulfide replacement process being deep but slow. After effectively separating manganese and zinc, the pH of their precipitation is controlled separately to prepare their respective products.

[0070] S5, manganese precipitate

[0071] Add a manganese-precipitating alkaline solution to the liquid after deep zinc precipitation, and control the pH at the reaction endpoint to be 9.0-9.5. After the reaction is complete, perform solid-liquid separation to obtain manganese hydroxide.

[0072] Manganese hydroxide can be produced by controlling the pH of the solution after deep zinc precipitation, thus realizing the recovery and utilization of manganese.

[0073] Optionally, in this step, the manganese precipitating alkaline solution is a sodium hydroxide solution.

[0074] Optionally, to ensure a complete reaction, the reaction can continue for 30–90 minutes (e.g., 30 minutes, 60 minutes, or 90 minutes) after the addition of the manganese precipitating alkali solution.

[0075] S6, Manganese Powder Recycling

[0076] The zinc-manganese slag is mixed with a sufficient amount of zinc-dissolving alkaline solution and reacted. After the reaction is completed, solid-liquid separation is performed to obtain manganese slag and zinc-dissolving liquid. The manganese slag is washed to obtain recycled manganese powder.

[0077] Optionally, the zinc dissolving alkali solution used in this step is a sodium hydroxide solution, ammonia water, or a mixture of the two.

[0078] To address the cost issue arising from the consumption of manganese powder during the process, this step utilizes an alkaline solution (ammonia and / or sodium hydroxide) to dissolve the zinc on the surface of the manganese powder. The chemical principles involved are shown in equations (6)-(9):

[0079]

[0080] Zn(s) + 4NH3 + 2H2O → [Zn(NH3)4] 2+ (q)+2OH - +H2↑ (7)

[0081]

[0082] Zn(OH)₂(s) + 4NH₃ → [Zn(NH)₃] 2+ (q)+2OH - (9)

[0083] Dissolving zinc on the surface of manganese powder with liquid alkali allows this key raw material (manganese powder) to be reused and regenerated, making the overall production and processing costs of the solution provided by this invention lower than those of extraction and purification.

[0084] Optionally, to ensure that the zinc on the surface of the zinc-manganese slag is fully dissolved, the mass ratio of zinc-manganese slag to zinc alkali solution is 1:1 to 20; further, the mass ratio of zinc-manganese slag to zinc alkali solution is 1:7 to 10 (e.g., 1:7, 1:8, 1:9, 1:10).

[0085] After treatment with the alkaline solution, the manganese powder is regenerated by washing with water or an acid solution. A preferred method is to use an acid solution for washing. Optionally, the acid solution used can be sulfuric acid, nitric acid, or hydrochloric acid; more preferably, a dilute sulfuric acid with a concentration of 0.05 mol / L is used.

[0086] S7, Crude Zinc Hydroxide

[0087] After the zinc solution is dissolved, the pH is adjusted to 7-8, and after sufficient reaction, solid-liquid separation is performed to obtain crude zinc hydroxide. The chemical principles involved are shown in equations (10) and (11):

[0088] ZnO 2- (q)+2H+ →Zn(OH)2(s) (10)

[0089]

[0090] Optionally, to ensure a complete reaction, after adjusting the pH to 7-8, the reaction time is continued for 50-70 minutes (e.g., 50 minutes, 60 minutes, or 70 minutes).

[0091] S8, Manganese Sulfide Regeneration

[0092] When the amount of residual manganese sulfide in the replacement manganese sulfide slag is sufficient to be reused in the second-stage zinc removal process to fully react with zinc ions in the zinc precipitation liquid, the replacement manganese sulfide slag will be reused in the second-stage zinc removal process.

[0093] Conversely, manganese sulfide regeneration is performed. For example, if the initial amount of manganese sulfide added is small, only enough for one reaction, it will be difficult to achieve sufficient zinc removal if reused. Or, if the initial amount of manganese sulfide added is large, and the zinc removal effect decreases significantly after multiple reuses, then manganese sulfide regeneration is performed.

[0094] The regeneration of manganese sulfide involves slurrying the replaced manganese sulfide slag, heating it to 90–110℃ and controlling the pH at 3–5, and then performing solid-liquid separation while hot. The resulting solid is the regenerated manganese sulfide, and the resulting liquid is a mixture of manganese sulfate and zinc sulfate. The copper-manganese solution separation and purification method provided in the example above employs non-extraction methods. By controlling the electrostatic precipitation of copper, combining manganese powder and manganese sulfide with zinc precipitation, and using liquid alkali to dissolve zinc and regenerate manganese powder, the valuable metals—copper, manganese, and zinc—in the copper-manganese solution are separated and purified, and corresponding products are prepared. The overall process has low cost and a simple flow, providing a new process route for the de-extraction of copper-manganese solution treatment in the metallurgical industry.

[0095] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0096] Example 1

[0097] Activated carbon degreasing: Take 5L of copper-manganese solution, the main components of which are Mn 69.1g / L, Cu 1.214g / L, Zn 9.072g / L, Ca 1.430g / L, Co 0.398g / L, Mg 0.0082g / L, Na 0.0163g / L, and oil 110.1mg / L; after adding 30g of activated carbon for degreasing, the oil concentration is reduced to 24.8mg / L.

[0098] Sulfide copper plating: Control the mechanical stirring speed to 400 r / min, adjust the pH to 1.1, add sodium sulfide solution until the redox potential is below 50 mV, continue the reaction for 30 minutes and then filter. The Cu in the filtrate is reduced to 0.0009 g / L to obtain the copper plating solution.

[0099] Zinc precipitation: Adjust the pH of the copper precipitation solution to about 5.0, add 70g of manganese powder, stir continuously for 1 hour, filter, and obtain zinc-manganese slag and zinc precipitation solution. The zinc content in the solution is reduced to 0.3242g / L, and the manganese content in the solution is 76.85g / L.

[0100] Deep zinc precipitation: Add 60g MnS to the zinc precipitation solution, control the reaction pH to about 5.5, and continue stirring for 1 hour to obtain the manganese sulfide slag and the deep zinc precipitation solution, which can further reduce zinc to 0.0022g / L solution.

[0101] The main components of the copper-manganese reverse solution after two-stage treatment are: Mn 75.85 g / L, Cu 0.0001 g / L, Zn 0.0023 g / L, Ca 1.529 g / L, Co 0.1311 g / L, Mg 0.0255 g / L, and Na 5.1538 g / L. The removal rates of Cu and Zu in the copper-manganese reverse solution both exceed 99.95%. The manganese sulfide was regenerated by boiling with sodium sulfide used in previous experiments, and then mixed with freshly prepared manganese sulfide.

[0102] Manganese powder reuse: Add 500 mL of 20% alkali solution to zinc-manganese slag, stir for 1 hour under mechanical stirring at 400 r / min, and filter to obtain a dark blue zinc-dissolving solution and crude manganese hydroxide. The main components of the dark blue zinc-dissolving solution are: Mn 0.0095 g / L, Cu 0.0004 g / L, Zn 26.65 g / L, Ca 0.0072 g / L, Co 0.0573 g / L, Mg 0.0004 g / L, Na 114.1 g / L. The manganese slag dissolved by alkali can be reused after simple water washing, and its main components are: Mn 52.92%, Zn 5.08%, Co 4.34%, Mg 0.021%, Ca 0.37%.

[0103] Manganese precipitation: 20% sodium hydroxide was added to the solution after deep zinc precipitation, and the pH of the solution was controlled at 9.0-9.5 to precipitate manganese. The mechanical stirring rate was 500 r / min. The resulting white solid was filtered, washed, and dried to obtain crude manganese hydroxide product, whose main components are: Mn 68.1%, Ca 0.022%, Fe 0.0049%, Ni 0.0057%, Cu 0.0122%, Pb 0.0012%, Mg 0.0097%, Co 0.0601%, Zn 0.0037%, Cd 0.0001%, K 0.0050%, As 0.0011%, Cr 0.0010%, and Na 1.061%.

[0104] Crude zinc hydroxide: A 2 mol / L sulfuric acid solution was added dropwise to the zinc-dissolving solution to control the pH at 7.5 for zinc precipitation. The mechanical stirring rate was 500 r / min. The resulting white solid was filtered, washed, and dried to obtain crude zinc hydroxide product. Its main components are: Mn 0.0052%, Ca 0.0019%, Fe 0.0073%, Ni 0.0008%, Cu 0.0001%, Pb 0.0009%, Mg 0.0003%, Co 0.0162%, Zn 74.85%, Cd 0.0001%, K 0.0086%, As 0.0001%, Na 0.0628%.

[0105] Example 2

[0106] Activated carbon degreasing: Take 2.5L of anti-copper-manganese solution, add 20g of activated carbon for degreasing, and its main components are: Cu 0.9841g / L, Mn 66.06g / L, Zn 8.41g / L, Co 0.3948g / L, Pb 0.0028g / L, Ca 1.313g / L, Mg 0.3750g / L, Fe 0.0099g / L, Cd 0.0213g / L, As 0.0015g / L, oil content is 12.53mg / L, and pH is 0.25.

[0107] Sulfide copper plating: The mechanical stirring speed is 400 r / min, the pH is adjusted to 1.22, sodium sulfide solution is added until the redox potential is below 50 mV, the reaction is continued for 20 minutes and then filtered. The Cu in the filtrate is reduced to 0.0013 g / L to obtain the copper plating solution.

[0108] Zinc precipitation: Adjust the pH of the copper precipitation solution to about 5.0, add 33g of manganese powder, stir continuously for 1 hour, filter, and obtain zinc-manganese slag and zinc precipitation solution. The zinc content in the solution is reduced to 0.7228g / L, and the manganese content in the solution is 76.53g / L.

[0109] Deep zinc precipitation: Add 14g MnS to the zinc precipitation solution, control the reaction pH to 5.0, and continue stirring for 30 minutes to obtain manganese sulfide slag and deep zinc precipitation solution, which can further reduce zinc to 0.0081g / L.

[0110] The main components of the copper-manganese precipitate after two-stage treatment are: Mn 71.92 g / L, Cu 0.0001 g / L, Zn 0.0081 g / L, Ca 1.266 g / L, Co 0.0002 g / L, Mg 0.0114 g / L, Fe 0.0050 g / L, Pb 0.0084 g / L, and Na 5.881 g / L. The removal rates of Cu and Zu in the copper-manganese precipitate both reach 99.9%. Manganese sulfide is prepared on-site from the after-situ manganese precipitation in the two-stage process, and a portion of the recycled manganese sulfide slag is mixed in. The copper slag produced in the above steps has a Cu content of 57.89%; the main components of the manganese slag produced are: Mn 22.44%, Zn 45.98%, and Co 2.415%.

[0111] Manganese powder reuse: 330 mL of 20% alkali solution was added to zinc-manganese slag, and the mixture was stirred for 1 hour under mechanical stirring at 400 r / min. The solution was filtered to obtain the zinc-dissolved liquid, whose main components were: Mn 0.0179 g / L, Cu 0.0001 g / L, Zn 45.97 g / L, Ca 0.0167 g / L, Co 0.0138 g / L, Mg 0.0004 g / L, Fe 0.0011 g / L, Pb 0.0001 g / L, and Na 86.45 g / L. The zinc-manganese slag dissolved by the alkali solution was simply washed with water, and then soaked and washed with 0.05 mol / L sulfuric acid solution at a solid-liquid ratio of 1:10. The main components of the resulting recycled manganese powder were: Mn 48.80%, Zn 7.01%, Co 5.44%, and Fe 2.846%.

[0112] Manganese precipitation: A 20% sodium hydroxide solution (by mass) was added to the solution after deep zinc precipitation. The pH of the solution was controlled at 9.0–9.5 to precipitate manganese. The mechanical stirring rate was 500 r / min. The resulting white solid was filtered, washed, and dried to obtain crude manganese hydroxide product. Its main components are: Mn 66.16%, Ca 0.0145%, Fe 0.0049%, Ni 0.0071%, Cu 0.0004%, Pb 0.0001%, Mg 0.0025%, Co 0.0002%, Zn 0.0098%, Cd 0.0001%, K 0.0045%, As 0.0015%, and Na 0.0087%.

[0113] Crude zinc hydroxide: A 2 mol / L sulfuric acid solution is added dropwise to the zinc-dissolving solution to control the pH at 7.5 for zinc precipitation. The mechanical stirring speed is 500 r / min. The resulting white solid is filtered, washed, and dried to obtain crude zinc hydroxide product. Its main components are: Mn 0.0486%, Ca 0.017%, Fe 0.0066%, Ni 0.0047%, Cu 0.0001%, Pb 0.0014%, Mg 0.0015%, Co 0.0203%, Zn 73.19%, Cd 0.0001%, K 0.0050%, As 0.0001%, and Na 0.0405%.

[0114] Example 3

[0115] Activated carbon degreasing: Take 1L of anti-copper-manganese solution, add 10g of activated carbon for degreasing, and its main components are: Cu 1.218g / L, Mn 49.27g / L, Zn 7.965g / L, Co 0.5456g / L, Pb 0.0032g / L, Ca 1.773g / L, Mg 0.0420g / L, Fe 0.0114g / L, Cd 0.0106g / L, As 0.0005g / L, oil content is 15.88mg / L, and pH is 0.18.

[0116] Sulfide copper plating: The mechanical stirring speed is 400 r / min, the pH is adjusted to 1.02, sodium sulfide solution is added until the redox potential is below 50 mV, the reaction is continued for 20 minutes and then filtered. The Cu in the filtrate is reduced to 0.0003 g / L to obtain the copper plating solution.

[0117] Zinc precipitation: Adjust the pH of the copper precipitation solution to about 5.0, add 14g of manganese powder, stir continuously for 60 minutes, filter, and obtain zinc-manganese slag and zinc precipitation solution. The zinc content in the solution is reduced to 0.2670g / L, and the manganese content in the solution is 51.26g / L.

[0118] Deep zinc precipitation: Add 6g MnS to the zinc precipitation solution, control the reaction pH to 5.0, and continue stirring for 30 minutes to obtain manganese sulfide slag and deep zinc precipitation solution, which can further reduce zinc to 0.0081g / L.

[0119] The main components of the copper-manganese precipitate after two-stage treatment are: Mn 52.11 g / L, Cu 0.0001 g / L, Zn 0.0064 g / L, Ca 1.566 g / L, Co 0.0014 g / L, Mg 0.0304 g / L, Fe 0.0002 g / L, Pb 0.0034 g / L, and Na 4.775 g / L. The removal rates of Cu and Zu in the copper-manganese precipitate both reach 99.9%. Manganese sulfide is prepared immediately after the second-stage manganese precipitation. The copper slag produced by the above steps has a Cu content of 52.13%; the main components of the manganese slag produced are: Mn 30.57%, Zn 40.22%, and Co 2.301%.

[0120] Manganese powder reuse: 100 mL of 20% alkali solution was added to zinc-manganese slag, and the mixture was stirred for 1 hour under mechanical stirring at 400 r / min. The solution was filtered to obtain the zinc-dissolved liquid, whose main components were: Mn 0.0213 g / L, Cu 0.0001 g / L, Zn 55.74 g / L, Ca 0.0227 g / L, Co 0.0120 g / L, Mg 0.0003 g / L, Fe 0.0005 g / L, Pb 0.0001 g / L, and Na 89.72 g / L. The zinc-manganese slag dissolved by the alkali solution was simply washed with water, and then soaked and washed with 0.05 mol / L sulfuric acid solution at a solid-liquid ratio of 1:10. The main components of the resulting recycled manganese powder were: Mn 56.78%, Zn 3.01%, Co 3.24%, and Fe 1.96%.

[0121] Manganese precipitation: 20% sodium hydroxide was added to the solution after deep zinc precipitation, and the pH of the solution was controlled at 9.0-9.5 to precipitate manganese. The mechanical stirring speed was 500 r / min. The resulting white solid was filtered, washed, and dried to obtain crude manganese hydroxide product, the main components of which are: Mn 64.05%, Ca 0.0085%, Fe 0.0061%, Ni 0.0031%, Cu 0.0002%, Pb 0.0001%, Mg 0.0009%, Co 0.0001%, Zn 0.008%, Cd 0.0001%, K 0.0083%, As 0.0006%, Na 0.0155%.

[0122] Crude zinc hydroxide: A 2 mol / L sulfuric acid solution is added dropwise to the zinc-dissolving solution to control the pH at 7.5 for zinc precipitation. The mechanical stirring speed is 500 r / min. The resulting white solid is filtered, washed, and dried to obtain crude zinc hydroxide product. Its main components are: Mn 0.0262%, Ca 0.092%, Fe 0.0009%, Ni 0.0058%, Cu 0.0001%, Pb 0.0006%, Mg 0.0007%, Co 0.0193%, Zn 72.53%, Cd 0.0001%, K 0.0064%, As 0.0001%, and Na 0.0832%.

[0123] Example 4

[0124] Activated carbon degreasing: Take 1L of anti-copper-manganese solution, add 10g of activated carbon for degreasing, and its main components are: Cu 1.263g / L, Mn 54.61g / L, Zn 8.779g / L, Co 0.5387g / L, Pb 0.0049g / L, Ca 1.815g / L, Mg 0.0326g / L, Fe 0.0066g / L, Cd 0.0039g / L, As 0.0002g / L, oil content is 13.42mg / L, and pH is 0.13.

[0125] Sulfide copper plating: The mechanical stirring speed is 400 r / min, the pH is adjusted to 1.06, sodium sulfide solution is added until the redox potential is below 50 mV, the reaction is continued for 20 minutes and then filtered. The Cu in the filtrate is reduced to 0.0023 g / L to obtain the copper plating solution.

[0126] Zinc precipitation: Adjust the pH of the copper precipitation solution to about 4.0, add 15g of manganese powder, stir continuously for 1 hour, filter, and obtain zinc-manganese slag and zinc precipitation solution. The zinc content in the solution is reduced to 0.2387g / L, and the manganese content in the solution is 53.81g / L.

[0127] Deep zinc precipitation: Add 7g MnS to the zinc precipitation solution, control the reaction pH to about 5.0, and continue stirring for 30 minutes to obtain manganese sulfide slag and deep zinc precipitation solution, which can further reduce zinc to 0.0036g / L.

[0128] The main components of the copper-manganese precipitate after two-stage treatment are: Mn 53.31 g / L, Cu 0.0003 g / L, Zn 0.0073 g / L, Ca 1.405 g / L, Co 0.0231 g / L, Mg 0.0254 g / L, Fe 0.0005 g / L, Pb 0.0003 g / L, and Na 5.792 g / L. The removal rates of Cu and Zu in the copper-manganese precipitate both reach 99.9%. Manganese sulfide is prepared immediately after the second-stage manganese precipitation. The copper slag produced by the above steps has a Cu content of 53.66%; the main components of the manganese slag produced are: Mn 33.906%, Zn 27.52%, and Co 3.727%.

[0129] Manganese powder reuse: 100 mL of 20% alkali solution was added to zinc-manganese slag, and the mixture was stirred for 1 hour under mechanical stirring at 400 r / min. The solution was filtered to obtain the zinc-dissolved liquid, whose main components were: Mn 0.0530 g / L, Cu 0.0001 g / L, Zn 40.24 g / L, Ca 0.0327 g / L, Co 0.0170 g / L, Mg 0.0019 g / L, Fe 0.0009 g / L, Pb 0.0001 g / L, and Na 82.43 g / L. The manganese slag obtained after dissolving in alkali was simply washed with water, and then soaked and washed with 0.05 mol / L sulfuric acid solution at a solid-liquid ratio of 1:10. The main components of the resulting recycled manganese powder were: Mn 52.45%, Zn 9.81%, and Co 1.86%.

[0130] Manganese precipitation: 20% sodium hydroxide was added to the solution after deep zinc precipitation, and the pH of the solution was controlled at 9.0-9.5 to precipitate manganese. The mechanical stirring speed was 500 r / min. The resulting white solid was filtered, washed, and dried to obtain crude manganese hydroxide product, the main components of which are: Mn 8.25%, Ca 0.0008%, Fe 0.0091%, Ni 0.0061%, Cu 0.0001%, Pb 0.0001%, Mg 0.0012%, Co 0.0019%, Zn 0.005%, Cd 0.0001%, K 0.0006%, As 0.0005%, Na 0.0582%.

[0131] Crude zinc hydroxide: A 2 mol / L sulfuric acid solution is added dropwise to the zinc-dissolving solution to control the pH at 7.5 for zinc precipitation. The mechanical stirring speed is 500 r / min. The resulting white solid is filtered, washed, and dried to obtain crude zinc hydroxide product. Its main components are: Mn 0.0095%, Ca 0.0685%, Fe 0.0012%, Ni 0.0008%, Cu 0.0001%, Pb 0.0005%, Mg 0.0013%, Co 0.0733%, Zn 0.23%, Cd 0.0001%, K 0.0048%, As 0.0001%, and Na 0.1448%.

[0132] Example 6

[0133] This embodiment is basically the same as Embodiment 1, except that: during the zinc precipitation process, the pH of the solution after copper precipitation is adjusted to about 6.0, and after adding manganese powder for zinc precipitation, the zinc content is reduced to 0.2254 g / L, and the concentrations of other metal ions are Mn 74.52 g / L, Cu 0.0001 g / L, Co 0.0106 g / L, Ca 1.120 g / L, Mg 0.0263 g / L, and the zinc removal rate in the first stage has reached 97.58%.

[0134] Example 7

[0135] This embodiment is basically the same as embodiment 3, except that: during the deep zinc precipitation process, the pH of the zinc precipitation solution is adjusted to about 4.0, 7.0g of manganese sulfide is added, and after reacting for 30 minutes, the zinc content of the zinc precipitation solution is reduced to 0.0170g / L.

[0136] Example 8

[0137] This embodiment is basically the same as embodiment 3, except that: during the deep zinc precipitation process, the pH of the zinc precipitation solution is adjusted to about 6.0, 7.0g of manganese sulfide is added, and after reacting for 30 minutes, the zinc content of the zinc precipitation solution is reduced to 0.0065g / L.

[0138] Comparative Example 1

[0139] This comparative example is basically the same as Example 3, except that the pH of the solution after copper precipitation was adjusted to approximately 7.0 during the zinc precipitation process. The results showed that the concentrations of Mn, Cu, and Zn in the solution after zinc precipitation were 35.88 g / L, 0.0001 g / L, and 0.0064 g / L. This indicates that the pH during zinc precipitation should not be too high; if it exceeds 6, it will lead to excessive manganese precipitation and manganese loss.

[0140] Comparative Example 2

[0141] This comparative example is essentially the same as Example 3, except that the pH of the post-zinc precipitation solution was adjusted to approximately 3 during the deep zinc precipitation process. The results showed that the post-zinc precipitation solution contained 55.59 g / L Mn, 0.0001 g / L Cu, and 1.0002 g / L Zn. This indicates that the pH during zinc precipitation should not be too low; if it falls below 4, the zinc removal rate will be too low, far below the 95% or higher zinc precipitation rate.

[0142] Comparative Example 3

[0143] This embodiment is basically the same as Embodiment 2, except that: during the deep zinc precipitation process, the pH of the post-precipitation solution was adjusted to approximately 7.0, and 14.0 g of manganese sulfide was added. After reacting for 30 minutes, the zinc content in the post-precipitation solution decreased to 0.0042 g / L, but the manganese content also decreased to 52.88 g / L. This indicates that the pH during the deep zinc precipitation process should not be too high. If it exceeds 6, although it will not affect the zinc precipitation effect, it will lead to excessive manganese precipitation and manganese loss.

[0144] Comparative Example 4

[0145] This embodiment is basically the same as Embodiment 2, except that: during the deep zinc precipitation process, the pH of the post-precipitation solution was adjusted to approximately 3.0, and 14.0 g of manganese sulfide was added. After reacting for 30 minutes, the zinc content in the post-precipitation solution decreased to 0.0042 g / L, while the manganese content increased to 78.85 g / L. However, a large amount of hydrogen sulfide gas was produced during the reaction, and a significant amount of manganese sulfide was lost after the reaction. This indicates that the pH should not be lower than 4.0 during the deep zinc precipitation process; otherwise, the side reaction of hydrogen sulfide production will be very serious.

[0146] Comparative Example 5

[0147] This implementation case is basically the same as Case 2, except that manganese sulfide is used directly for zinc precipitation. After adding 28g of manganese sulfide and reacting for 1 hour, the zinc content decreased to 5.828g / L, indicating that manganese sulfide cannot be used for the treatment of high-concentration zinc.

[0148] In summary, the method provided in this embodiment of the invention first precipitates copper and then zinc. Because the solubility product of copper sulfide precipitate is much smaller than that of zinc sulfide and manganese sulfide, the potential control range is large, and precise control is not required for copper precipitation. The overall process of this method is also more concise. The replacement reaction using manganese powder is fast and efficient, and it does not introduce other impurities, consumes no other auxiliary materials, and has low cost. Sufficient manganese powder can be used to treat copper-manganese solutions with high zinc content. After the zinc precipitation step, zinc-manganese slag is leached with alkali, and the pH of the leaching solution (post-zinc precipitation solution) is adjusted to within 7-8 to produce zinc hydroxide, which can realize resource recycling.

[0149] The preferred embodiments of the present invention have the following advantages:

[0150] 1. This method effectively separates copper, manganese, and zinc from copper-manganese solutions using a novel, non-extraction approach, and prepares the corresponding manganese hydroxide and zinc hydroxide products. Compared to extraction methods for treating copper-manganese solutions, this method has a simpler overall process, achieves comparable separation and purification results, and is more cost-effective and less polluting.

[0151] 2. Compared with direct precipitation of metal elements in copper-manganese solutions, this method realizes the resource utilization of manganese, copper, and zinc in copper-manganese solutions. In particular, manganese and zinc ions cannot be separated by direct precipitation, but the two-stage zinc precipitation method using manganese powder and manganese sulfide achieves effective separation of manganese and zinc and can produce products with high purity.

[0152] 3. By using a two-stage process combining manganese powder and manganese sulfide for zinc precipitation, it solves the problems of manganese powder replacement process being fast but not deep, and manganese sulfide replacement process being deep but slow. After effectively separating manganese and zinc, the pH of their precipitation is controlled to achieve the preparation of their respective products.

[0153] 4. By using an alkaline solution to dissolve the zinc and zinc hydroxide on the surface of zinc-manganese slag, manganese powder can be reused, and a high-zinc solution can be obtained to prepare zinc hydroxide, further reducing the processing cost.

[0154] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing hydroxides using an anticopper-manganese solution, characterized in that, include: Sulfide copper precipitation: Adjust the pH of the reverse copper manganese solution to the range of 1.0~1.2, then add sodium sulfide solution, control the potential of the reverse copper manganese solution to 0~50 mV to carry out sulfide copper precipitation, and obtain copper precipitation solution; Zinc precipitation: Adjust the pH of the copper precipitation solution to 4-6, mix the copper precipitation solution with manganese powder, perform manganese-zinc replacement, and after full reaction, obtain zinc-manganese slag and zinc precipitation solution; Deep zinc precipitation step: The pH of the zinc precipitation solution is maintained within 4 to 6. Manganese sulfide is added to the zinc precipitation solution. After the zinc ions react fully with the manganese sulfide, the displacement manganese sulfide slag and the deep zinc precipitation solution are obtained. Manganese precipitation step: Add manganese precipitation alkaline solution to the liquid after zinc precipitation at the specified depth, and control the pH at the reaction endpoint to be 9.0 ~ 9.

5. After the reaction is complete, perform solid-liquid separation to obtain manganese hydroxide. Crude zinc hydroxide: The zinc-manganese slag is mixed with a sufficient amount of zinc-dissolving alkaline solution and reacted. After solid-liquid separation, manganese slag and zinc-dissolving liquid are obtained. The pH of the zinc-dissolving liquid is adjusted to 7-8. After sufficient reaction, solid-liquid separation is performed to obtain zinc hydroxide.

2. The method according to claim 1, characterized in that, The preparation method also includes a manganese powder reuse step: washing the manganese slag to obtain recycled manganese powder, which can be directly reused in the zinc precipitation step.

3. The method according to claim 1, characterized in that, The replaced manganese sulfide slag is sufficient to be reused in the deep zinc precipitation step, and reacts fully with the residual zinc ions in the zinc precipitation liquid. Therefore, the replaced manganese sulfide slag is used as manganese sulfide that reacts with zinc ions for reuse.

4. The method according to claim 3, characterized in that, The sum of the amount of manganese powder added during the zinc precipitation process and the amount of manganese sulfide added during the deep zinc precipitation process is 1.5 to 5.0 times the zinc ion equivalent in the copper-manganese solution.

5. The method according to claim 3, characterized in that, It also includes at least one of the following features (1) to (5): (1) During the zinc precipitation process, the pH is adjusted to 4 to 6; (2) The amount of manganese powder added is 1.0 to 2.0 times the zinc ion equivalent in the anti-copper manganese solution; (3) During the deep zinc precipitation process, the pH is adjusted to 4.5 ~ 5.5; (4) The amount of manganese sulfide added is 0.4 to 0.6 times the zinc ion equivalent in the anti-copper manganese solution; (5) The replacement manganese sulfide slag is reused 5 to 10 times.

6. The method according to any one of claims 1 to 5, characterized in that, During the zinc plating process, the copper plating solution is mixed with manganese powder and stirred at 300-400 r / min for 0.5-1.5 h.

7. The method according to any one of claims 3 to 5, characterized in that, The manganese sulfide was added dropwise to the zinc precipitation solution using a slurry-like process.

8. The method according to claim 7, characterized in that, During the deep zinc immersion process, the addition of manganese sulfide to the zinc immersion solution is carried out under stirring at a speed of 300 to 400 r / min. After the manganese sulfide is added, the stirring reaction continues for 0.5 to 1.5 h.

9. The method according to any one of claims 1 to 5, characterized in that, The manganese precipitation alkaline solution used in the manganese precipitation process is a sodium hydroxide solution.

10. The method according to any one of claims 1 to 5, characterized in that, After the manganese alkali solution is added dropwise, continue the reaction for 30-90 minutes.

11. The method according to any one of claims 1 to 5, characterized in that, In the preparation of crude zinc hydroxide, the zinc-dissolving alkaline solution used is sodium hydroxide solution, ammonia water, or a mixture of the two.

12. The method according to any one of claims 1 to 5, characterized in that, The mass ratio of the zinc-manganese slag to the zinc alkali solution is 1:1 to 20.

13. The method according to any one of claims 1 to 5, characterized in that, The mass ratio of the zinc-manganese slag to the zinc alkali solution is 1:7 to 10.

14. The method according to claim 2, characterized in that, The substance used to wash the manganese slag is water or a dilute acid solution.

15. The method according to any one of claims 1 to 5, characterized in that, The specific process of copper plating with sulfide is as follows: Under a stirring rate of 300-400 r / min, sodium hydroxide solution is added dropwise to adjust the pH of the copper-manganese solution to the range of 1.0-1.

2. Then, sodium sulfide solution is added dropwise. When the potential drops to 0-50 mV, the addition is stopped, and stirring is continued for 25-35 min. During the stirring process, Na2S solution is added dropwise to control the potential to maintain 0-50 mV. After stirring is completed, solid-liquid separation is performed to obtain copper slag and the copper-precipitated liquid.

16. The method according to claim 15, characterized in that, The added sodium sulfide solution has a molar concentration of 0.5~1.5 mol / L.

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