Method for efficiently separating metal elements from manganese salt solution

Abstract

The present invention relates to a method for efficiently separating metal elements from a manganese-containing salt solution, and belongs to the technical field of chemical metallurgy. The method for efficiently separating metal elements from a manganese-containing salt solution comprises: for a manganese-containing salt solution containing vanadium, process route 1 is adopted; for a manganese-containing salt solution not containing vanadium, process route 2 is adopted; the vanadium content in the manganese-containing salt solution is above 0.2wt.%. The process of the present invention is simple, the production efficiency is high, and the cost is low. Compared with other manganese-containing solutions that recover valuable metals, the manganese carbonate obtained by the present invention is a high-purity product, which meets the Class II standard of HG / T2836-2011 and has greater economic value.

Description

Technical Field

[0001] The invention relates to a method for efficiently separating metal elements from a manganese-containing salt solution, belonging to the technical field of chemical metallurgy. Background Art

[0002] Manganese is a basic metal raw material, which is widely used in the fields of steel industry, building materials, lightweight materials, chemicals, medicine, new energy, etc. It is a basic raw material for promoting sustainable economic and social development. Since steel production is inseparable from manganese, manganese has become a strategic resource for any country. In recent years, due to low-carbon development, the battery industry has expanded rapidly, and there is no viable substitute for manganese in the industry, resulting in an increasing demand for manganese. Therefore, the recovery of manganese from manganese-containing salt solutions has broad application prospects.

[0003] The sources of manganese-containing salt solutions are complex and diverse. In recent years, people have conducted a lot of research on recovering manganese from different solutions, and have also spawned many recovery methods. The extraction-precipitation method can be used as a preferred method for recovering manganese due to its advantages of good selectivity, low production cost, high product purity, recyclable extractant, no pollution, economic and environmental protection, and high efficiency. The manganese-containing salt solution of the present invention mainly includes two types: a vanadium-containing salt solution and a vanadium-free salt solution.

[0004] The vanadium-containing salt solution mainly comes from the vanadium extraction process of vanadium-titanium magnetite. Since vanadium-titanium magnetite contains not only vanadium but also a large amount of manganese, this part of manganese coexists with vanadium in the qualified vanadium precipitation liquid after roasting, leaching and other processes, and then is separated from vanadium in the precipitation process. Therefore, high-manganese vanadium-containing wastewater will inevitably be produced during the vanadium precipitation process. Limestone is mostly used to precipitate the metal ions in production, resulting in serious waste of manganese resources.

[0005] Vanadium-free salt solution mainly comes from manganese ore leaching, but the leaching solution contains a large amount of impurity ions such as iron, magnesium, and calcium. If high-purity manganese products are to be prepared, impurity removal treatment must be carried out. However, the current impurity removal preparation process is lengthy and complicated, and the efficiency is low. The recovery of high-purity manganese still faces challenges.

[0006] Patent CN102070198A discloses a method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reducing and leaching pyrolusite with iron filings. It uses a neutralization method to adjust the pH value to 5-6 to hydrolyze the trivalent iron in the solution into ferric hydroxide precipitation. After filtration, the manganese sulfate primary filtrate and filter residue are obtained. The primary filtrate is first added with a sulfiding agent for sulfidation to remove heavy metal ions, and then a fluoriding agent is added to remove calcium, magnesium and other ions in the solution. The solution is allowed to stand and then the precipitate is removed. The purified solution is added with ammonium carbonate to prepare high-purity manganese carbonate, and the filtrate is concentrated and then ammonium sulfate is recovered. Although this method is suitable for the development and utilization of pyrolusite of different tastes, the filtrate cannot be returned to the system, resulting in the discharge of wastewater, and the fluoriding agent is used to remove calcium, magnesium will introduce fluoride ion impurities, and the presence of fluoride ions in the system is not conducive to the preparation of subsequent high-purity products.

[0007] Patent CN109706316A discloses a method for recovering valuable metals from vanadium precipitation mother liquor, using solvent extraction to recover vanadium, and carbonate method to select precipitated manganese and magnesium respectively. Although this method can effectively recover valuable metals, the extraction and impurity removal effect of P204 is poor during the extraction process, and the vanadium-containing organic phase is stripped with sulfuric acid, which will make the manganese ion impurity content in the vanadium-rich solution too high, affecting the purity of V2O5. Sodium sulfite is added in the reduction step, which will introduce sodium ion impurities and affect the purity of subsequent products. Although the magnesium precipitation liquid after adding carbonate to precipitate manganese and magnesium has a low impurity ion content, the pH is high and cannot be directly returned to leaching. Multiple pH adjustments not only increase production costs, but also lengthy process flows, which will greatly reduce production efficiency in actual production, thereby hindering its industrial development.

[0008] Patent CN115478178A discloses a method for efficiently extracting vanadium and manganese from vanadium precipitation mother liquor in vanadium slag calcination roasting acid leaching of vanadium, comprising the following steps: (1) placing vanadium slag calcination roasting clinker into manganese extraction residual water, adding dilute sulfuric acid to obtain acid leaching solution, adding ammonium salt to the acid leaching solution to obtain vanadium precipitation mother liquor, and adjusting the pH of the vanadium precipitation mother liquor to 2.0-3.0 to obtain vanadium extraction stock solution; (2) extracting vanadate anions in the vanadium extraction stock solution to obtain vanadium extraction residual water; (3) adjusting the pH of the vanadium extraction residual water to 4.5-5.0 to obtain manganese extraction stock solution; (4) countercurrently extracting manganese ions in the manganese extraction stock solution to obtain manganese extraction residual water; (5) recycling steps (1) to (4) to separate and extract vanadium and manganese therein until the magnesium ion concentration in the manganese extraction residual water reaches 25 g / L, using lime to neutralize and precipitate the magnesium ions in the manganese extraction residual water, and returning the neutralized water as the water source for the acid leaching solution of vanadium slag calcination roasting clinker. Although this invention does not generate any wastewater, it uses two extractants. After multiple cycles, the two extractants will inevitably be entrained with each other, affecting the extraction effect. In addition, the pH value needs to be constantly adjusted during the process, which not only increases the production cost, but also makes the process lengthy and complicated, which is not conducive to industrial implementation.

[0009] Patent CN114381619A discloses a method for preparing high-purity trimanganese tetraoxide and high-purity magnesium oxide, the method comprising the following steps: (1) leaching manganese ore to prepare a manganese-containing solution; (2) performing impurity removal treatment; (3) separating manganese and magnesium in the purified solution by extraction, manganese entering the organic phase and magnesium remaining in the raffinate; (4) stripping the loaded organic phase with an alkali solution to obtain a regenerated organic phase and a stripping solution; (5) filtering the stripping solution to obtain manganese sulfate, and drying to obtain a high-purity manganese sulfate product; (6) adding ammonia water to the raffinate for precipitation to obtain magnesium hydroxide and ammonium sulfate solution, washing the magnesium hydroxide and calcining to obtain a high-purity magnesium oxide product; (7) evaporating the ammonium sulfate solution to obtain an ammonium sulfate product. This patent uses alkaline stripping to achieve efficient preparation of high-purity manganese tetraoxide and high value-added utilization of magnesium. However, when the alkaline stripping solution is returned to the leached manganese ore, sulfuric acid solution needs to be added to adjust the pH, resulting in a lengthy and complicated process. The ammonium sulfate solution after magnesium precipitation cannot be directly recycled, and evaporation and crystallization increase energy consumption and costs, and cause a waste of some water resources and a depreciation of ammonium sulfate.

[0010] Patent CN115725866A discloses a method for preferentially recovering manganese from waste lithium-rich manganese-based positive electrode materials, the method comprising: step 1) roasting and leaching, mixing the waste lithium-rich manganese-based positive electrode materials with ammonium sulfate and then roasting at a low temperature, leaching the roasted product with water and then performing solid-liquid separation to obtain a roasted leaching solution; step 2) complexing and separating manganese, adding ammonium sulfite to the roasting leaching solution obtained in step 1), performing a complexing reaction, and obtaining a manganese-rich slag; step 3) oxidative leaching, adding an oxidant to the manganese-rich slag obtained in step 2) for oxidative leaching, and adjusting the solution pH to obtain an oxidized leaching solution; step 4) extraction and stripping, performing multi-stage extraction of manganese on the oxidized leaching solution obtained in step 3) to obtain a manganese-loaded organic phase and a raffinate; stripping the manganese-loaded organic phase to obtain a manganese sulfate solution. Although this invention can effectively reduce the negative impact of lithium, nickel and cobalt on manganese extraction during the extraction process, the manganese-containing leaching solution needs to go through processes such as complexation and separation of manganese - oxidation leaching - extraction - stripping, and the reaction process requires the addition of oxidants and adjustment of pH, resulting in a complex process and difficulty in industrialization. In addition, no specific recovery method is proposed for other metal ions.

[0011] In summary, the existing technology for economically and effectively recovering metal elements from manganese-containing salt solutions still faces problems such as high recovery costs, complicated processes, and manganese is rarely considered a qualified product. Summary of the invention

[0012] The object of the present invention is a method for efficiently separating metal elements from a manganese salt solution.

[0013] To achieve the purpose of the present invention, the method for efficiently separating metal elements from a manganese salt solution comprises:

[0014] For the manganese salt solution containing vanadium, process route-1 is adopted; for the manganese salt solution not containing vanadium, process route-2 is adopted; the vanadium content in the manganese salt solution containing vanadium is more than 0.2wt.%;

[0015] The process route-1 includes:

[0016] A1. adding an extractant to a manganese salt solution, and extracting the mixed metal-loaded organic phase and the raffinate;

[0017] B1. The metal-loaded organic phase in step A1 is mixed with a stripping agent 1, and the stripping phases are stripped to obtain a manganese-containing stripping solution and a vanadium-loaded organic phase;

[0018] C1. Preparation of manganese products:

[0019] Preparation of manganese carbonate: adding a manganese precipitant to the manganese-containing stripping solution in step B1, and adjusting the pH to 6.0-8.5, stirring the reaction, aging, and solid-liquid separation to obtain manganese carbonate solid and manganese precipitation supernatant;

[0020] Preparation of ammonium manganese sulfate: placing the manganese-containing stripping solution in step B1 at -10°C to 15°C for crystallization, allowing it to stand for aging after the crystallization is completed and filtering it while it is cold to obtain ammonium manganese sulfate and manganese precipitation supernatant, and drying at low temperature to obtain ammonium manganese sulfate;

[0021] In step B1, the vanadium-loaded organic phase is mixed with a stripping agent, and stripping and phase separation is performed to obtain a vanadium-containing stripping solution and a lean organic phase;

[0022] The process route-2 includes:

[0023] A2. adding an extractant to the manganese salt solution, and extracting the mixed metal-loaded organic phase and the raffinate;

[0024] B2. The metal-loaded organic phase in step A2 is mixed with a low concentration ammonium sulfate solution, and the phases are stripped to obtain an ammonium sulfate solution containing magnesium and calcium and an organic phase loaded with manganese;

[0025] C2. The ammonium sulfate solution containing magnesium and calcium is subjected to solid-liquid separation to obtain calcium sulfate solid and magnesium-containing ammonium sulfate solution, the ammonium sulfate solution containing magnesium is returned to step B2, the organic phase loaded with metal in step A2 is stripped, and after the magnesium ion enrichment in the ammonium sulfate solution reaches 13 g / L, magnesium ammonium sulfate crystals and magnesium precipitation supernatant are obtained by cooling and crystallizing;

[0026] The organic phase loaded with manganese in step B2 is uniformly mixed with a high-concentration ammonium sulfate solution, and the phases are separated by back extraction to obtain a manganese-containing ammonium sulfate solution and an iron-containing organic phase. A manganese precipitant is added to the manganese-containing ammonium sulfate solution, and the pH is adjusted to 6.0-8.5. After stirring for reaction, aging and solid-liquid separation are performed to obtain a manganese carbonate solid and a manganese precipitation supernatant;

[0027] Among them, the volume ratio of the extractant to the manganese salt solution in steps A1 and A2 is 5:1 to 1:5, the stirring intensity of the extraction is 50 to 3000 rpm, the extraction temperature is 20 to 70° C., and the preferred stirring intensity is 50 to 800 rpm.

[0028] In a specific embodiment, the manganese salt solution includes at least one of the vanadium precipitation mother liquor after calcium vanadium extraction, manganese-containing raffinate after calcium roasting leaching liquor extraction, manganese ore leaching liquor, or stone coal and manganese ore co-leaching liquor. The raffinate of steps A1 and A2 can be returned to the acid leaching step for use.

[0029] In a specific embodiment, the extractant in steps A1 and A2 includes at least one of an organic phosphorus extractant, an organic phosphine extractant, an organic sulfonic acid extractant, an organic carboxylic acid extractant, and a tertiary carbonic acid extractant; preferably, the extractant includes at least one of di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphate 2-ethylhexyl ester, di(2,4,4-trimethylpentyl) hypophosphorous acid, 2-ethylhexyl phosphonic acid mono(2-ethylhexyl) ester, N,NN-n-octylamine dimethylenephenylphosphonic acid, N,NN-n-hexylamine dimethylenephenylphosphonic acid, toluenesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, cinnamic acid, fatty acid, lauric acid, and cycloalkane acid.

[0030] In a specific embodiment, the stripping agent 1 in step B1 is a high-concentration ammonium sulfate solution, or a vanadium-containing ammonium sulfate + sulfuric acid composite solution;

[0031] When the stripping agent 1 is a high-concentration ammonium sulfate solution, the concentration of the high-concentration ammonium sulfate solution of B1 and C2 is 20-40wt.%, the volume ratio of the ammonium sulfate solution to the metal-loaded organic phase or the manganese-loaded organic phase is 8:1-1:8, the stripping time is 10-60min, the stirring intensity of the stripping is 50-3000rpm, and the stripping temperature is 20-70°C. Preferably, the concentration of the high-concentration ammonium sulfate solution of B1 and C2 is 30-35wt.%, preferably, the volume ratio of the ammonium sulfate solution to the metal-loaded organic phase or the manganese-loaded organic phase is 1:1-1:3, and the stirring intensity of the stripping is 50-800rpm; preferably, the number of stages of the countercurrent stripping of the ammonium sulfate solution of B1 and the metal-loaded organic phase ranges from 1 to 5;

[0032] When the stripping agent 1 is a composite solution of vanadium-containing ammonium sulfate + sulfuric acid, the concentration of ammonium sulfate in the stripping agent 1 is 15-35wt.%, the concentration of sulfuric acid is 5%-10%, the concentration of vanadium-containing ions is 0.2wt.%-0.4wt.%, the volume ratio of the stripping agent 1 to the organic phase loaded with manganese is 1:2-1:8, the stripping time is 10-60min, the stripping stirring intensity is 50-800rpm, and the stripping temperature is 20-70°C.

[0033] In a specific embodiment, the low concentration ammonium sulfate concentration of B2 is 5 to 15 wt.%, the volume ratio of the metal-loaded organic phase to the low concentration ammonium sulfate solution is 1:8 to 8:1, the stripping time is 10 to 60 min, the stripping stirring intensity is 50 to 3000 ppm, the stripping temperature is 20 to 70 ° C, and preferably the volume ratio of the metal-loaded organic phase to the low concentration ammonium sulfate solution is 1:3 to 2:1.

[0034] When the stripping agent 1 is a high-concentration ammonium sulfate solution, the manganese precipitant is a carbonate solution, and the carbonate solution preferably includes at least one of ammonium bicarbonate solution, ammonium carbonate solution, sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution, and carbon dioxide; the molar ratio of carbonate contained in the added manganese precipitant to manganese ions in the solution is 1:1 to 2:1, and the pH of the precipitation is adjusted to a preset value of 6.0 to 8.5, and more preferably the molar ratio of carbonate to manganese ions in the solution is 1.3 to 1.5:1;

[0035] When the stripping agent 1 is a composite solution of ammonium sulfate containing vanadium + sulfuric acid, the manganese ammonium sulfate product is prepared by cooling crystallization, the crystallization temperature is -10 to 15°C, the crystallization time is 1 to 4 hours, the aging time is 10 to 40 minutes, the drying temperature is 60 to 80°C, and the preferred crystallization temperature is 0 to 10°C.

[0036] In a specific embodiment, the stripping agent in step C1 is at least one of 1-30wt.% sulfuric acid solution, 2-10wt.% oxalic acid solution or 1-14wt.% ammonium oxalate solution, the volume ratio of the vanadium-loaded organic phase to the stripping agent solution is 1:8-8:1, the stripping time is 10-60min, the stripping stirring intensity is 50-3000ppm, the stripping temperature is 20-70°C, preferably the volume ratio of the vanadium-loaded organic phase to the stripping agent solution is 1:3-2:1, and the stripping stirring intensity is 50-800rpm.

[0037] In a specific embodiment, the process route-1 also includes the preparation of vanadium pentoxide:

[0038] Method 1. The vanadium-containing stripping solution is introduced into ammonia water, the pH is adjusted to a range of 7.5 to 8.5, and after stirring for 1 to 2 hours, solid-liquid separation is performed to obtain ammonium metavanadate solid, and the ammonium metavanadate solid is calcined to obtain vanadium pentoxide;

[0039] Method 2. or the vanadium-containing stripping solution is continuously introduced into an ammonium sulfate solution at 90 to 100 ° C, the pH is adjusted to a preset range, and after reacting for 1 to 2 hours, the solid-liquid separation is performed to obtain a polyvanadate solid, and the polyvanadate solid is calcined to obtain vanadium pentoxide;

[0040] The concentration of the ammonium sulfate solution continuously introduced in method 2 of preferred process route-1 is 100-400 g / L, the introduction time is 5-10 min, the introduction temperature range is 90-100° C., and the pH range is adjusted to 1.7-1.9.

[0041] In a specific embodiment, the process route-2 further comprises:

[0042] Method 1. The iron-containing organic phase is mixed evenly with the oxalic acid solution, and the phases are stripped to obtain an iron-containing oxalic acid solution and a lean organic phase. The iron-containing oxalic acid solution is treated with ultraviolet light to obtain ferrous oxalate precipitation, and solid-liquid separation is performed to obtain ferrous oxalate;

[0043] Method 2. The iron-containing organic phase is mixed evenly with the ammonium oxalate solution, and the phases are stripped to obtain an iron-containing ammonium oxalate solution and a lean organic phase. Ammonia water is passed through the iron-containing ammonium oxalate solution to adjust the pH value to a range of 3 to 4. After the reaction, solid-liquid separation is performed to obtain iron hydroxide;

[0044] Preferably, the oxalic acid concentration of method 1 of process route 2 is 5 to 20 wt.%, the stripping temperature is 30 to 70° C., and the volume ratio of the iron-containing organic phase to the oxalic acid solution is 1:8 to 8:1.

[0045] In a specific embodiment, the method further includes returning the lean organic phase to step A1 or A2 for recycling as an extractant; preferably, it also includes returning the manganese precipitation supernatant in step C2 for use as a high-concentration ammonium sulfate solution; returning the magnesium precipitation supernatant in step C2 for use as a low-concentration ammonium sulfate solution; and returning the manganese precipitation supernatant in step C1 for use as a stripping agent 1.

[0046] In a specific embodiment, if ammonium oxalate solution is used as the stripping agent in step C2, sulfuric acid solution is required to wash the ammonium ions entrained in the extractant during the regeneration of the lean organic phase. When the ammonium ions in the sulfuric acid solution reach a certain concentration, ammonium sulfate crystals are precipitated by cooling and crystallization. If oxalic acid solution is used as the stripping agent, there is no need to wash the ammonium ions.

[0047] The solid product obtained by the present invention can be dried, for example, the manganese carbonate solid can be further dried. The solid-liquid separation of the present invention can be a conventional solid-liquid separation method such as filtration and centrifugation.

[0048] Beneficial effects:

[0049] 1. The process of the present invention is simple, the production efficiency is high and the cost is low.

[0050] 2. Compared with other methods for recovering valuable metals from manganese-containing solutions, the manganese carbonate obtained in the present invention is a high-purity product, conforms to the Class II standard of HG / T2836-2011, and has greater economic value.

[0051] 3. The extractant and stripping agent used in the present invention can be recycled, and the raffinate after extraction with the manganese salt solution can be returned to the acid leaching step, thereby achieving zero discharge of wastewater, avoiding environmental pollution and the cost of wastewater treatment. The metal elements circulate in the system, and theoretically there is no loss, which is in line with the concept of green development.

[0052] 4. The present invention adopts different stripping agents to classify and recover the metal elements in the manganese salt solution in a stepwise manner, so that the metal elements can be effectively separated and utilized at a high value.

[0053] 5. The present invention selects ammonium sulfate solution as the stripping agent to strip and extract manganese. Compared with the commonly used sulfuric acid stripping agent, the ammonium sulfate solution has higher selectivity for manganese and avoids the problem of too low pH value and increased carbonate ion consumption during precipitation of manganese carbonate. While achieving efficient separation of vanadium and manganese, the economic cost is reduced.

[0054] 6. The present invention selects a vanadium-containing ammonium sulfate + sulfuric acid composite solution as a stripping agent, so that manganese can be completely stripped while vanadium is not stripped. Further stripping and separation are performed, and the impurity content in the obtained stripping solution is low, and the prepared vanadium pentoxide has high purity. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 The present invention is a process flow chart of a specific embodiment of the present invention. DETAILED DESCRIPTION

[0056] To achieve the purpose of the present invention, the method for efficiently separating metal elements from a manganese salt solution comprises:

[0057] For the manganese salt solution containing vanadium, process route-1 is adopted; for the manganese salt solution not containing vanadium, process route-2 is adopted; the vanadium content in the manganese salt solution containing vanadium is more than 0.2wt.%;

[0058] The process route-1 includes:

[0059] A1. adding an extractant to a manganese salt solution, and extracting the mixed metal-loaded organic phase and the raffinate;

[0060] B1. The metal-loaded organic phase in step A1 is mixed with a stripping agent 1, and the stripping phases are stripped to obtain a manganese-containing stripping solution and a vanadium-loaded organic phase;

[0061] C1. Preparation of manganese products:

[0062] Preparation of manganese carbonate: adding a manganese precipitant to the manganese-containing stripping solution in step B1, and adjusting the pH to 6.0-8.5, stirring the reaction, aging, and solid-liquid separation to obtain manganese carbonate solid and manganese precipitation supernatant;

[0063] Preparation of ammonium manganese sulfate: placing the manganese-containing stripping solution in step B1 at -10°C to 15°C for crystallization, allowing it to stand for aging after the crystallization is completed and filtering it while it is cold to obtain ammonium manganese sulfate and manganese precipitation supernatant, and drying at low temperature to obtain ammonium manganese sulfate;

[0064] In step B1, the vanadium-loaded organic phase is mixed with a stripping agent, and stripping and phase separation is performed to obtain a vanadium-containing stripping solution and a lean organic phase;

[0065] The process route-2 includes:

[0066] A2. adding an extractant to the manganese salt solution, and extracting the mixed metal-loaded organic phase and the raffinate;

[0067] B2. The metal-loaded organic phase in step A2 is mixed with a low concentration ammonium sulfate solution, and the phases are stripped to obtain an ammonium sulfate solution containing magnesium and calcium and an organic phase loaded with manganese;

[0068] C2. The ammonium sulfate solution containing magnesium and calcium is subjected to solid-liquid separation to obtain calcium sulfate solid and magnesium-containing ammonium sulfate solution, the ammonium sulfate solution containing magnesium is returned to step B2, the organic phase loaded with metal in step A2 is stripped, and after the magnesium ion enrichment in the ammonium sulfate solution reaches 13 g / L, magnesium ammonium sulfate crystals and magnesium precipitation supernatant are obtained by cooling and crystallizing;

[0069] The organic phase loaded with manganese in step B2 is uniformly mixed with a high-concentration ammonium sulfate solution, and the phases are separated by back extraction to obtain a manganese-containing ammonium sulfate solution and an iron-containing organic phase. A manganese precipitant is added to the manganese-containing ammonium sulfate solution, and the pH is adjusted to 6.0-8.5. After stirring for reaction, aging and solid-liquid separation are performed to obtain a manganese carbonate solid and a manganese precipitation supernatant;

[0070] Among them, the volume ratio of the extractant to the manganese salt solution in steps A1 and A2 is 5:1 to 1:5, the stirring intensity of the extraction is 50 to 3000 rpm, the extraction temperature is 20 to 70° C., and the preferred stirring intensity is 50 to 800 rpm.

[0071] In a specific embodiment, the manganese salt solution includes at least one of the vanadium precipitation mother liquor after calcium vanadium extraction, manganese-containing raffinate after calcium roasting leaching liquor extraction, manganese ore leaching liquor, or stone coal and manganese ore co-leaching liquor. The raffinate of steps A1 and A2 can be returned to the acid leaching step for use.

[0072] In a specific embodiment, the extractant in steps A1 and A2 includes at least one of an organic phosphorus extractant, an organic phosphine extractant, an organic sulfonic acid extractant, an organic carboxylic acid extractant, and a tertiary carbonic acid extractant; preferably, the extractant includes at least one of di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphate 2-ethylhexyl ester, di(2,4,4-trimethylpentyl) hypophosphorous acid, 2-ethylhexyl phosphonic acid mono(2-ethylhexyl) ester, N,NN-n-octylamine dimethylenephenylphosphonic acid, N,NN-n-hexylamine dimethylenephenylphosphonic acid, toluenesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, cinnamic acid, fatty acid, lauric acid, and cycloalkane acid.

[0073] In a specific embodiment, the stripping agent 1 in step B1 is a high-concentration ammonium sulfate solution, or a vanadium-containing ammonium sulfate + sulfuric acid composite solution;

[0074] When the stripping agent 1 is a high-concentration ammonium sulfate solution, the concentration of the high-concentration ammonium sulfate solution of B1 and C2 is 20-40wt.%, the volume ratio of the ammonium sulfate solution to the metal-loaded organic phase or the manganese-loaded organic phase is 8:1-1:8, the stripping time is 10-60min, the stirring intensity of the stripping is 50-3000rpm, and the stripping temperature is 20-70°C. Preferably, the concentration of the high-concentration ammonium sulfate solution of B1 and C2 is 30-35wt.%, preferably, the volume ratio of the ammonium sulfate solution to the metal-loaded organic phase or the manganese-loaded organic phase is 1:1-1:3, and the stirring intensity of the stripping is 50-800rpm; preferably, the number of stages of the countercurrent stripping of the ammonium sulfate solution of B1 and the metal-loaded organic phase ranges from 1 to 5;

[0075] When the stripping agent 1 is a composite solution of vanadium-containing ammonium sulfate + sulfuric acid, the concentration of ammonium sulfate in the stripping agent 1 is 15-35wt.%, the concentration of sulfuric acid is 5%-10%, the concentration of vanadium-containing ions is 0.2wt.%-0.4wt.%, the volume ratio of the stripping agent 1 to the organic phase loaded with manganese is 1:2-1:8, the stripping time is 10-60min, the stripping stirring intensity is 50-800rpm, and the stripping temperature is 20-70°C.

[0076] In a specific embodiment, the low concentration ammonium sulfate concentration of B2 is 5 to 15 wt.%, the volume ratio of the metal-loaded organic phase to the low concentration ammonium sulfate solution is 1:8 to 8:1, the stripping time is 10 to 60 min, the stripping stirring intensity is 50 to 3000 ppm, the stripping temperature is 20 to 70 ° C, and preferably the volume ratio of the metal-loaded organic phase to the low concentration ammonium sulfate solution is 1:3 to 2:1.

[0077] When the stripping agent 1 is a high-concentration ammonium sulfate solution, the manganese precipitant is a carbonate solution, and the carbonate solution preferably includes at least one of ammonium bicarbonate solution, ammonium carbonate solution, sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution, and carbon dioxide; the molar ratio of carbonate contained in the added manganese precipitant to manganese ions in the solution is 1:1 to 2:1, and the pH of the precipitation is adjusted to a preset value of 6.0 to 8.5, and more preferably the molar ratio of carbonate to manganese ions in the solution is 1.3 to 1.5:1;

[0078] When the stripping agent 1 is a composite solution of ammonium sulfate containing vanadium + sulfuric acid, the manganese ammonium sulfate product is prepared by cooling crystallization, the crystallization temperature is -10 to 15°C, the crystallization time is 1 to 4 hours, the aging time is 10 to 40 minutes, the drying temperature is 60 to 80°C, and the preferred crystallization temperature is 0 to 10°C.

[0079] In a specific embodiment, the stripping agent in step C1 is at least one of 1-30wt.% sulfuric acid solution, 2-10wt.% oxalic acid solution or 1-14wt.% ammonium oxalate solution, the volume ratio of the vanadium-loaded organic phase to the stripping agent solution is 1:8-8:1, the stripping time is 10-60min, the stripping stirring intensity is 50-3000ppm, the stripping temperature is 20-70°C, preferably the volume ratio of the vanadium-loaded organic phase to the stripping agent solution is 1:3-2:1, and the stripping stirring intensity is 50-800rpm.

[0080] In a specific embodiment, the process route-1 also includes the preparation of vanadium pentoxide:

[0081] Method 1. The vanadium-containing stripping solution is introduced into ammonia water, the pH is adjusted to a range of 7.5 to 8.5, and after stirring for 1 to 2 hours, solid-liquid separation is performed to obtain ammonium metavanadate solid, and the ammonium metavanadate solid is calcined to obtain vanadium pentoxide;

[0082] Method 2. or the vanadium-containing stripping solution is continuously introduced into an ammonium sulfate solution at 90 to 100 ° C, the pH is adjusted to a preset range, and after reacting for 1 to 2 hours, the solid-liquid separation is performed to obtain a polyvanadate solid, and the polyvanadate solid is calcined to obtain vanadium pentoxide;

[0083] The concentration of the ammonium sulfate solution continuously introduced in method 2 of preferred process route-1 is 100-400 g / L, the introduction time is 5-10 min, the introduction temperature range is 90-100° C., and the pH range is adjusted to 1.7-1.9.

[0084] In a specific embodiment, the process route-2 further comprises:

[0085] Method 1. The iron-containing organic phase is mixed evenly with the oxalic acid solution, and the phases are stripped to obtain an iron-containing oxalic acid solution and a lean organic phase. The iron-containing oxalic acid solution is treated with ultraviolet light to obtain ferrous oxalate precipitation, and solid-liquid separation is performed to obtain ferrous oxalate;

[0086] Method 2. The iron-containing organic phase is mixed evenly with the ammonium oxalate solution, and the phases are stripped to obtain an iron-containing ammonium oxalate solution and a lean organic phase. Ammonia water is passed through the iron-containing ammonium oxalate solution to adjust the pH value to a range of 3 to 4. After the reaction, solid-liquid separation is performed to obtain iron hydroxide;

[0087] Preferably, the oxalic acid concentration of method 1 of process route 2 is 5 to 20 wt.%, the stripping temperature is 30 to 70° C., and the volume ratio of the iron-containing organic phase to the oxalic acid solution is 1:8 to 8:1.

[0088] In a specific embodiment, the method further includes returning the lean organic phase to step A1 or A2 for recycling as an extractant; preferably, it also includes returning the manganese precipitation supernatant in step C2 for use as a high-concentration ammonium sulfate solution; returning the magnesium precipitation supernatant in step C2 for use as a low-concentration ammonium sulfate solution; and returning the manganese precipitation supernatant in step C1 for use as a stripping agent 1.

[0089] In a specific embodiment, if ammonium oxalate solution is used as the stripping agent in step C2, sulfuric acid solution is required to wash the ammonium ions entrained in the extractant during the regeneration of the lean organic phase. When the ammonium ions in the sulfuric acid solution reach a certain concentration, ammonium sulfate crystals are precipitated by cooling and crystallization. If oxalic acid solution is used as the stripping agent, there is no need to wash the ammonium ions.

[0090] The solid product obtained by the present invention can be dried, for example, the manganese carbonate solid can be further dried. The solid-liquid separation of the present invention can be a conventional solid-liquid separation method such as filtration and centrifugation.

[0091] The specific implementation modes of the present invention are further described below in conjunction with embodiments, but the present invention is not limited to the scope of the embodiments.

[0092] Example 1

[0093] The manganese salt solution in this embodiment is derived from high-manganese and vanadium-containing wastewater generated during the vanadium extraction process.

[0094] (1) Extraction: 2153.24 g of high-manganese-containing vanadium wastewater was taken and subjected to three-stage countercurrent extraction with 3399.86 g of extractant P-15 at 60° C. The extraction temperature was 60° C., the feed rate of high-manganese-containing vanadium wastewater was 40 mL / min, the feed rate of the extractant was 80 mL / min, and the stirring speed of the extraction centrifuge was 3000 rpm. After the reaction was completed, 3358.52 g of an organic phase loaded with vanadium and manganese and 2063.57 g of a raffinate phase were obtained.

[0095] (2) Stripping 1: 1914.67 g of 35% by mass ammonium sulfate solution and 2743.45 g of the loaded organic phase in (1) were mixed uniformly at 60° C. and subjected to single-stage stripping with a stirring intensity of 400 rpm and a stripping time of 30 min. The mixture was then separated by a separating funnel to obtain 1915.23 g of manganese-containing ammonium sulfate solution and 2742.64 g of a lean organic phase.

[0096] (3) Manganese precipitation: Add 105.23 g of 30% ammonium carbonate solution to the ammonium sulfate solution obtained in step (2), adjust the pH to 7.0, mix well at room temperature, react for 4 h, age for 3 h after the reaction, and then filter with a circulating water vacuum pump to obtain 1891.06 g of filtrate and 28 g of manganese carbonate filter cake. The obtained manganese carbonate filter cake is dried in an oven at 100° C. for 3 h.

[0097] (4) Stripping 2: 1823.75 g of the extractant after five cycles in step (2) and 1154.23 g of 5% ammonium oxalate were stirred and mixed at 50° C. with a stirring intensity of 350 rpm and a reaction time of 30 min. The mixture was then filtered through a separatory funnel to obtain 1805.43 g of a lean organic phase and 1139.45 g of a vanadium-containing ammonium oxalate solution.

[0098] (5) Vanadium precipitation: dilute ammonia water is slowly introduced into the ammonium oxalate stripping solution obtained in step (4) by a peristaltic pump to adjust the pH of the solution, the ammonia flow rate is 5 ml / min, the pH is adjusted to 7.99, and then the reaction is carried out at 50° C. under low-speed stirring for 1 h, and then filtered by a circulating water vacuum pump. The obtained ammonium metavanadate is dried in a vacuum drying oven at 80° C. for 12 h, and then calcined at 580° C. for 2 h to finally obtain the product vanadium pentoxide.

[0099] The experimental results are shown in Table 1.

[0100] Table 1 Experimental data of Example 1

[0101]

[0102] Table 2 Manganese carbonate product quality

[0103]

[0104] Table 3 Laboratory vanadium pentoxide product quality

[0105] <![CDATA[V2O5]]> <![CDATA[Na2O+K2O]]> Si Fe P S As National Standard ≥99 ≤1 ≤0.15 ≤0.2 ≤0.03 ≤0.01 ≤0.01 product 99.93 0.002 0.003 0.005 0.001 0.006 0.002

[0106] The experimental results show that after three-stage countercurrent extraction, the extraction rates of vanadium and manganese are 90.00% and 71.02% respectively. After stripping with ammonium sulfate solution, the stripping rates of vanadium and manganese are 4.61% and 61.04% respectively. It can be proved that the recovery and separation of vanadium and manganese can be well achieved through co-extraction-stripping separation. The introduction of carbonate ions into a manganese enriched solution with a content of 0.483% can achieve a manganese precipitation rate of more than 97.72%, and the manganese grade of the obtained manganese carbonate product is 45.71%, and its impurity content meets the standard of Type II qualified products in HG / T2836-2011. Through alkaline precipitation of vanadium, the vanadium pentoxide product obtained meets the requirements of the metallurgical industry for high-purity vanadium pentoxide in GB3283-1987.

[0107] Example 2

[0108] The manganese salt solution in this embodiment is derived from high-manganese and vanadium-containing wastewater generated during the vanadium extraction process.

[0109] (1) Extraction: 2155.43 g of high-manganese-containing vanadium wastewater was taken and subjected to three-stage countercurrent extraction with 4251.34 g of extractant P204 at 60° C. The extraction temperature was 60° C., the feed rate of high-manganese-containing vanadium wastewater was 50 mL / min, and the feed rate of the extractant was 100 mL / min. After the reaction was completed, 2135.76 g of raffinate and 4201.45 g of an organic phase loaded with vanadium and manganese were obtained.

[0110] (2) Stripping 1: 2789.74 g of 35% by mass ammonium sulfate solution and 4199.56 g of the loaded organic phase in (1) were subjected to three-stage countercurrent stripping. The stripping temperature was 50° C., the feed rate of the ammonium sulfate solution was 40 mL / min, and the feed rate of the organic phase was 80 mL / min. After the reaction, 2644.89 g of manganese-containing ammonium sulfate solution and 4170.67 g of lean organic phase were obtained.

[0111] (3) Manganese precipitation: Add 113.27 g of 30% ammonium carbonate solution to the ammonium sulfate solution obtained in step (2), adjust the pH to 7.0, mix well at room temperature, react for 4 h, age for 3 h after the reaction, and then filter with a circulating water vacuum pump to obtain 2604.34 g of filtrate and 33.14 g of manganese carbonate filter cake. The obtained manganese carbonate filter cake is dried in an oven at 100° C. for 3 h.

[0112] (4) Stripping 2: 1763.54 g of the extractant after five cycles in step (2) and 1121.03 g of 5% ammonium oxalate were stirred and mixed at 50° C. with a stirring intensity of 400 rpm and a reaction time of 30 min. The mixture was then filtered through a separatory funnel to obtain 1760.43 g of a lean organic phase and 1119.95 g of a vanadium-containing ammonium oxalate solution.

[0113] (5) Vanadium precipitation: dilute ammonia water is slowly introduced into the ammonium oxalate stripping solution obtained in step (4) by a peristaltic pump to adjust the pH of the solution, the ammonia flow rate is 5 ml / min, the pH is adjusted to 8.02, and then the reaction is carried out at 50° C. under low-speed stirring for 1 h, and then filtered by a circulating water vacuum pump. The obtained ammonium metavanadate is dried in a vacuum drying oven at 80° C. for 12 h, and then calcined at 580° C. for 2 h to finally obtain the product vanadium pentoxide.

[0114] The experimental results are shown in Table 4.

[0115] Table 4 Experimental data of Example 2

[0116]

[0117] Table 5 Manganese carbonate product quality

[0118]

[0119]

[0120] The experimental results show that after three-stage countercurrent extraction, the extraction rates of vanadium and manganese are 90.01% and 69.34%, respectively. The stripping rates of vanadium and manganese by 35wt.% ammonium sulfate solution are 7.04% and 93.24%, respectively. Compared with Example 1, after three-stage countercurrent stripping, the stripping rate of manganese is significantly increased, while the stripping rate of vanadium changes less. By drawing the stripping equilibrium isotherm of stripping manganese by 35wt.% ammonium sulfate solution, it is found that after three-stage countercurrent extraction, the extraction rate of manganese can reach more than 90%. Therefore, the three-stage countercurrent stripping can better recover manganese and is more conducive to the enrichment of the subsequent manganese precipitation solution.

[0121] Example 3

[0122] The manganese salt solution of this embodiment is derived from the sulfuric acid leaching solution of manganese ore. Its raw material composition is shown in Table 6:

[0123] Table 6 Manganese ore leaching solution full table

[0124] element Mn Mg Fe Ca Content (g / L) 43.8 3.32 8.23 1.45

[0125] (1) Extraction: 1985.78 g of a manganese-containing salt solution was subjected to three-stage countercurrent extraction with 3521.76 g of an extractant P-15 at 60° C. The extraction temperature was 60° C., the feed rate of the manganese-containing salt solution was 40 mL / min, the feed rate of the extractant was 80 mL / min, and the extraction phases were separated to obtain a raffinate and an organic phase loaded with manganese.

[0126] (2) Stripping 1: The organic phase loaded above is mixed with a 6% ammonium sulfate solution by volume ratio O / A=1, the stirring intensity is 500 rpm, the reaction time is 30 min, the reaction temperature is 60°C, and then the phases are separated by a separatory funnel to obtain a magnesium-containing ammonium sulfate solution and an organic phase. The obtained magnesium-containing ammonium sulfate solution is evaporated and concentrated, filtered, and calcium sulfate is obtained; the filtrate is cooled and crystallized at 15°C to obtain magnesium ammonium sulfate crystals.

[0127] (3) Stripping 2: The organic phase obtained in step (2) was mixed uniformly with a 35% by mass ammonium sulfate solution at a volume ratio of O / A=2, with a stirring intensity of 500 rpm, a reaction time of 30 min, and a reaction temperature of 60°C, and then phase separation was performed using a separatory funnel to obtain a manganese-containing ammonium sulfate solution and an iron-loaded organic phase.

[0128] (4) Manganese precipitation: The manganese-containing ammonium sulfate solution obtained in step (3) is stirred and mixed with ammonium bicarbonate at a molar ratio of 1.5, and reacted at a pH of 7.0 for 4 hours. After the reaction is completed, the mixture is aged for 3 hours, and then filtered to obtain a manganese carbonate precipitate and an ammonium sulfate filtrate.

[0129] (5) Stripping 3: The organic phase obtained in step (3) is mixed uniformly with an oxalic acid solution having a mass fraction of 8% at a volume ratio of O / A=2, the stirring intensity is 450 rpm, the reaction time is 30 min, the reaction temperature is 60°C, and then the phases are separated to obtain an oxalic acid solution containing iron and a lean organic phase. The obtained oxalic acid solution containing iron is irradiated with ultraviolet light to obtain a ferrous oxalate precipitate. The lean organic phase is washed with dilute oxalic acid having a concentration of 1.5 wt.% in two-stage countercurrent at a temperature of 60°C and a volume ratio of O / A=4, the oxalic acid entrained in the lean organic phase is recovered, the phases are separated to obtain a regenerated extractant, and the extractant is returned to step (1) for recycling.

[0130] Table 7 Experimental data of Example 3

[0131]

[0132] It can be seen from the experimental data that the extraction rate of manganese can reach more than 55%, the extraction rate of iron can reach more than 85%, the extraction rates of magnesium and calcium can reach 14% and 40% respectively, and the separation of Mn from Mg and Ca can be achieved by using ammonium sulfate solutions of different concentrations. The stripping rates of manganese and iron using 35wt.% ammonium sulfate solution and 8wt.% oxalic acid solution can reach more than 90%, which can well realize the recovery of manganese and magnesium.

[0133] Example 4

[0134] The manganese salt solution in this embodiment is derived from high-manganese and vanadium-containing wastewater generated during the vanadium extraction process.

[0135] (1) Extraction: 1277.31 g of high-manganese and vanadium-containing wastewater was mixed with 1053.22 g of extractant P15 at a stirring intensity of 500 rpm, a reaction temperature of 50° C., and a reaction time of 30 min. After the reaction was completed, the mixture was poured into a separating funnel for phase separation to obtain 1055.25 g of metal ion-loaded extractant and 1271.92 g of raffinate.

[0136] (2) Stripping: a composite solution with an ammonium sulfate concentration of 25 wt.%, a sulfuric acid concentration of 8 wt.%, and a vanadium ion concentration of 0.33 wt.% was prepared as a stripping agent, 257.46 g of the composite solution and 1055.25 g of the metal ion-loaded extractant in (1) were stirred and mixed at a stirring intensity of 500 rpm, a reaction temperature of 50° C., and a reaction time of 30 min. After the reaction was completed, the mixture was poured into a separating funnel for phase separation to obtain 1029.56 g of the metal ion-loaded extractant and 265.33 g of stripping solution.

[0137] (3) Cooling crystallization: The stripping solution obtained in (2) was placed in a jacketed beaker and reacted in a constant temperature water bath at 0°C for 2 h. After the reaction was completed, the solution was allowed to stand for half an hour and filtered while cold. The obtained solid was dried at 70°C for 4 h to obtain ammonium manganese sulfate.

[0138] The experimental results are shown in Table 8.

[0139] Table 8 Experimental data of Example 4

[0140]

[0141] The experimental results show that when 8wt.% sulfuric acid + 25wt.% ammonium sulfate + 0.33wt.% composite solution is used as a stripping agent to strip the vanadium-loaded manganese extractant, the stripping rate of manganese is >90%, while the stripping rate of vanadium is only 2.87%. Most of the vanadium remains in the extractant, achieving the separation of vanadium and manganese, and most of the manganese and magnesium are stripped out, leaving only vanadium in the extractant, creating a good foundation for the subsequent stripping-precipitation of vanadium to prepare high-purity vanadium pentoxide. When cooling and crystallizing at 0°C, the crystallization rate of manganese is >70%, and vanadium hardly crystallizes out, so when the supernatant of manganese precipitation is returned as a stripping agent, there is no need to introduce vanadium for the second time, and the 0.33wt.% vanadium can be kept in the system for recycling.

[0142] Comparative Example 1

[0143] The experimental procedure refers to step (2) in Example 1. The same batch of extractants after three-stage countercurrent extraction loading was taken and divided into three equal parts. Under the same experimental conditions, they were stripped with 8% sulfuric acid solution, 35% ammonium sulfate solution, and 8% citric acid solution, respectively. The metal ion content in the aqueous phase and the stripping effect were compared. The experimental results are shown in Table 8.

[0144] Experimental conditions: stripping phase ratio O / A=2, stripping time 30min, stripping temperature 60°C, stirring intensity 400rpm.

[0145] Table 9 Stripping experimental data of different stripping agents

[0146]

[0147] The experimental results show that although the stripping rate of 8wt.% sulfuric acid for manganese is as high as over 90%, the stripping rate of vanadium is also very high while stripping manganese, resulting in too high vanadium impurity content in the stripping solution, and the separation effect of vanadium and manganese is not as good as ammonium sulfate solution. In addition, the vanadium concentration is too high, which is not conducive to the purity of the subsequent manganese carbonate product. Ammonium sulfate solution is the best stripping agent.

[0148] Comparative Example 2

[0149] Experimental Procedure Referring to step (2) in Comparative Example 1, the same batch of extractants loaded with vanadium and manganese were taken and divided into 5 equal parts. Under the same experimental conditions, the stripping ratio was changed. The experimental results are shown in Table 9.

[0150] Experimental conditions: stripping temperature of 60°C, reaction time of 30 min, stirring intensity of 400 rpm, and ammonium sulfate solution concentration of 35 wt.%.

[0151] Table 10 Different stripping comparison stripping experimental results

[0152]

[0153] The experimental results show that as the stripping ratio O / A decreases, the stripping rate of manganese increases continuously, but while the stripping ratio increases, the content of manganese ions in the stripping solution decreases continuously. When the stripping ratio is too large, the manganese stripping effect is poor and the reaction volume is too large, which is not conducive to industrial implementation. When the stripping ratio is too small, although the stripping ratio of manganese increases, the content of manganese ions in the stripping solution is low, which is not conducive to subsequent manganese enrichment and precipitation of manganese carbonate products. Combined with the equilibrium isotherm of stripping, the preferred stripping ratio is O / A=2, which can not only ensure that the stripping ratio is above 90%, but also reduce the difficulty of enrichment.

[0154] Comparative Example 3

[0155] The experimental steps were similar to step (3) in Example 2. The same batch of manganese-containing solution after stripping and enrichment was taken, and the molar ratio of carbonate to manganese ions was changed. The experimental results are shown in Table 10.

[0156] Experimental conditions: precipitation time 4h, mass fraction of ammonium carbonate solution added is 30%, precipitation temperature is room temperature (25°C), stirring intensity is 350rpm, and aging is 3h.

[0157] Table 11 Experimental data under different carbon addition molar ratios

[0158] <![CDATA[Addition amount of ammonium carbonate (nCO3: nMn)]]> Manganese precipitation rate (%) Manganese content (%) 0.9 71.69 47.39 1 81.50 46.63 1.3 93.71 45.50 1.5 98.78 45.02 2 99.71 42.36

[0159] It can be seen from the experimental results that with the increase of the amount of ammonium carbonate added, the precipitation rate of manganese gradually increases, but at the same time, the purity of manganese carbonate continues to decrease. Since the stripping solution itself is acidic, if ammonium carbonate is added in a 1:1 ratio, part of the carbonate ions will become carbon dioxide and escape from the system, resulting in incomplete manganese precipitation. If the amount of ammonium carbonate added is too large, the pH value of the system will be too large, and vanadium and magnesium will precipitate in the form of ammonium metavanadate and magnesium hydroxide, affecting the purity of manganese carbonate. When the molar ratio of ammonium carbonate added is 1.5, the manganese precipitation rate reaches 98.78%, and the manganese grade reaches 45.02%, meeting the requirements for high-purity manganese carbonate in HG / T2836-2011. The molar ratio of ammonium carbonate added is preferably 1.3-1.5.

Claims

1. A method for efficiently separating metal elements from a manganese salt solution, characterized in that: The method comprises: For the manganese salt solution containing vanadium, process route-1 is adopted; for the manganese salt solution not containing vanadium, process route-2 is adopted; the vanadium content in the manganese salt solution containing vanadium is more than 0.2wt.%; The process route-1 includes: A1. adding an extractant to a manganese salt solution, and extracting the mixed metal-loaded organic phase and the raffinate; B1. Mixing the metal-loaded organic phase in step A1 with the first stripping agent, stripping and separating the phases to obtain a manganese-containing stripping solution and a vanadium-loaded organic phase; C1. Preparation of manganese products: Preparation of manganese carbonate: adding a manganese precipitant to the manganese-containing stripping solution in step B1, and adjusting the pH to 6.0-8.5, stirring the reaction, aging, and solid-liquid separation to obtain manganese carbonate solid and manganese precipitation supernatant; Preparation of ammonium manganese sulfate: placing the manganese-containing stripping solution in step B1 at -10°C to 15°C for cooling and crystallization, standing and aging after the crystallization, and filtering while cold to obtain ammonium manganese sulfate solid and manganese precipitation supernatant, and drying at low temperature to obtain ammonium manganese sulfate; In step B1, the vanadium-loaded organic phase is mixed with a second stripping agent, and stripping and phase separation are performed to obtain a vanadium-containing stripping solution and a lean organic phase; The process route-2 includes: A2. adding an extractant to the manganese salt solution, and extracting the mixed metal-loaded organic phase and the raffinate; B2. The metal-loaded organic phase in step A2 is mixed with a low concentration ammonium sulfate solution, and the phases are stripped to obtain an ammonium sulfate solution containing magnesium and calcium and an organic phase loaded with manganese; C2. The ammonium sulfate solution containing magnesium and calcium is subjected to solid-liquid separation to obtain calcium sulfate solid and magnesium-containing ammonium sulfate solution, the ammonium sulfate solution containing magnesium is returned to step B2, the organic phase loaded with metal in step A2 is stripped, and after the magnesium ion enrichment in the ammonium sulfate solution reaches 13 g / L, magnesium ammonium sulfate crystals and magnesium precipitation supernatant are obtained by cooling and crystallizing; The organic phase loaded with manganese in step B2 is uniformly mixed with a high-concentration ammonium sulfate solution, and the phases are separated by back extraction to obtain a manganese-containing ammonium sulfate solution and an iron-containing organic phase. A manganese precipitant is added to the manganese-containing ammonium sulfate solution, and the pH is adjusted to 6.0-8.

5. After stirring for reaction, aging and solid-liquid separation are performed to obtain a manganese carbonate solid and a manganese precipitation supernatant; Wherein, the volume ratio of the extractant to the manganese salt solution in steps A1 and A2 is 5:1 to 1:5, the stirring intensity of the extraction is 50 to 3000 rpm, and the extraction temperature is 20 to 70°C; The first stripping agent in step B1 is a high-concentration ammonium sulfate solution, or a vanadium-containing ammonium sulfate + sulfuric acid composite solution; When the first stripping agent is a high-concentration ammonium sulfate solution, the concentration of the high-concentration ammonium sulfate solution in B1 and C2 is 20-40wt.%, the volume ratio of the ammonium sulfate solution to the metal-loaded organic phase or the manganese-loaded organic phase is 8:1-1:8, the stripping time is 10-60min, the stripping stirring intensity is 50-3000rpm, and the stripping temperature is 20-70°C; When the first stripping agent is a composite solution of vanadium-containing ammonium sulfate + sulfuric acid, the concentration of ammonium sulfate in the first stripping agent is 15wt.%~35wt.%, the concentration of sulfuric acid is 5wt.%~10wt.%, the concentration of vanadium-containing ions is 0.2wt.%~0.4wt.%, the volume ratio of the first stripping agent to the organic phase loaded with manganese is 1:2~1:8, the stripping time is 10~60min, the stripping stirring intensity is 50~800rpm, and the stripping temperature is 20~70℃.

2. The method for efficiently separating metal elements from a manganese salt solution according to claim 1, characterized in that: The stirring intensity of the extraction in steps A1 and A2 is 50 to 800 rpm.

3. The method for efficiently separating metal elements from a manganese-containing salt solution according to claim 1, characterized in that: The manganese salt solution comprises at least one of vanadium precipitation mother liquor after calcium process vanadium extraction, manganese-containing raffinate after calcium process roasting leaching liquor extraction, manganese ore leaching liquor or co-leaching liquor of stone coal and manganese ore.

4. The method for efficiently separating metal elements from a manganese salt solution according to claim 1 or 2, characterized in that: The extractant in steps A1 and A2 includes at least one of an organic phosphorus extractant, an organic phosphine extractant, an organic sulfonic acid extractant, an organic carboxylic acid extractant, and a tert-butyl carbonic acid extractant.

5. The method for efficiently separating metal elements from a manganese-containing salt solution according to claim 4, characterized in that: The extractant in steps A1 and A2 includes at least one of di(2-ethylhexyl) phosphate, 2-ethylhexyl phosphate 2-ethylhexyl ester, di(2,4,4-trimethylpentyl) hypophosphorous acid, 2-ethylhexyl phosphonic acid mono(2-ethylhexyl) ester, N,NN-n-octylamine dimethylenephenylphosphonic acid, N,NN-n-hexylamine dimethylenephenylphosphonic acid, toluenesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, cinnamic acid, fatty acid, lauric acid, and cycloalkane acid.

6. The method for efficiently separating metal elements from a manganese salt solution according to claim 1 or 2, characterized in that: The concentration of the high concentration ammonium sulfate solution of B1 and C2 is 30-35 wt.%.

7. The method for efficiently separating metal elements from a manganese-containing salt solution according to claim 6, characterized in that: The volume ratio of the ammonium sulfate solution to the metal-loaded organic phase or the manganese-loaded organic phase is 1:1 to 1:3, and the stirring intensity of the stripping is 50 to 800 rpm.

8. The method for efficiently separating metal elements from a manganese-containing salt solution according to claim 6, characterized in that: The number of stages of countercurrent stripping between the ammonium sulfate solution in B1 and the metal-loaded organic phase ranges from 1 to 5.

9. The method for efficiently separating metal elements from a manganese-containing salt solution according to claim 1 or 2, characterized in that: The concentration of low-concentration ammonium sulfate in B2 is 5-15wt.%, the volume ratio of the metal-loaded organic phase to the low-concentration ammonium sulfate solution is 1:8-8:1, the stripping time is 10-60min, the stripping stirring intensity is 50-3000ppm, and the stripping temperature is 20-70°C.

10. The method for efficiently separating metal elements from a manganese-containing salt solution according to claim 9, characterized in that: The volume ratio of the metal-loaded organic phase to the low-concentration ammonium sulfate solution is 1:3 to 2:

1.

11. The method for efficiently separating metal elements from a manganese salt solution according to claim 1, characterized in that: When the first stripping agent is a high-concentration ammonium sulfate solution, the manganese precipitant is a carbonate solution; the molar ratio of carbonate contained in the added manganese precipitant to manganese ions in the solution is 1:1 to 2:1, and the pH of the precipitation is adjusted to a preset value of 6.0 to 8.5; When the first stripping agent is a composite solution of ammonium sulfate containing vanadium and sulfuric acid, the ammonium manganese sulfate product is prepared by cooling crystallization, the crystallization temperature is -10 to 15°C, the crystallization time is 1 to 4 hours, the aging time is 10 to 40 minutes, and the drying temperature is 60 to 80°C.

12. The method for efficiently separating metal elements from a manganese salt solution according to claim 11, characterized in that: The carbonate solution includes at least one of ammonium bicarbonate solution, ammonium carbonate solution, sodium carbonate solution, sodium bicarbonate solution and potassium carbonate solution.

13. The method for efficiently separating metal elements from a manganese salt solution according to claim 11, characterized in that: The molar ratio of carbonate in the carbonate solution to manganese ions in the solution is 1.3-1.5:

1.

14. The method for efficiently separating metal elements from a manganese salt solution according to claim 11, characterized in that: The crystallization temperature is 0-10°C.

15. The method for efficiently separating metal elements from a manganese salt solution according to claim 1 or 2, characterized in that: In step C1, the second stripping agent is at least one of a 1-30wt.% sulfuric acid solution, a 2-10wt.% oxalic acid solution or a 1-14wt.% ammonium oxalate solution, the volume ratio of the vanadium-loaded organic phase to the second stripping agent solution is 1:8-8:1, the stripping time is 10-60min, the stripping stirring intensity is 50-3000ppm, and the stripping temperature is 20-70°C.

16. The method for efficiently separating metal elements from a manganese salt solution according to claim 15, characterized in that: The volume ratio of the vanadium-loaded organic phase to the second stripping agent solution is 1:3-2:1, and the stirring intensity of the stripping is 50-800 rpm.

17. The method for efficiently separating metal elements from a manganese salt solution according to claim 1 or 2, characterized in that: The process route-1 also includes the preparation of vanadium pentoxide: Method 1: The vanadium-containing stripping solution is introduced into ammonia water, the pH is adjusted to a range of 7.5 to 8.5, and after stirring for 1 to 2 hours, solid-liquid separation is performed to obtain ammonium metavanadate solid, and the ammonium metavanadate solid is calcined to obtain vanadium pentoxide; Method 2: Alternatively, the vanadium-containing stripping solution is continuously introduced into an ammonium sulfate solution at 90-100° C., the pH is adjusted to a preset range, and after reacting for 1-2 hours, the solid-liquid separation is performed to obtain a polyvanadate solid, and the polyvanadate solid is calcined to obtain vanadium pentoxide.

18. The method for efficiently separating metal elements from a manganese salt solution according to claim 17, characterized in that: The concentration of the ammonium sulfate solution continuously introduced in the method 2 of the process route-1 is 100-400 g / L, the introduction time is 5-10 min, the introduction temperature range is 90-100° C., and the pH range is adjusted to 1.7-1.

9.

19. The method for efficiently separating metal elements from a manganese salt solution according to claim 1 or 2, characterized in that: The process route-2 also includes: Method 1. The iron-containing organic phase is mixed evenly with the oxalic acid solution, and the phases are stripped to obtain an iron-containing oxalic acid solution and a lean organic phase. The iron-containing oxalic acid solution is treated with ultraviolet light to obtain ferrous oxalate precipitation, and solid-liquid separation is performed to obtain ferrous oxalate; Method 2: The iron-containing organic phase is mixed evenly with the ammonium oxalate solution, and the phases are stripped to obtain the iron-containing ammonium oxalate solution and the lean organic phase. Ammonia water is passed into the iron-containing ammonium oxalate solution to adjust the pH value to 3 to 4. After the reaction, solid-liquid separation is performed to obtain ferric hydroxide.

20. The method for efficiently separating metal elements from a manganese-containing salt solution according to claim 19, characterized in that: The oxalic acid concentration of method 1 of process route 2 is 5 to 20 wt.%, the stripping temperature is 30 to 70° C., and the volume ratio of the iron-containing organic phase to the oxalic acid solution is 1:8 to 8:

1.

21. The method for efficiently separating metal elements from a manganese salt solution according to claim 19, characterized in that: The method further comprises returning the lean organic phase to step A1 or A2 for recycling as an extractant.

22. The method for efficiently separating metal elements from a manganese-containing salt solution according to claim 19, characterized in that: The method further comprises returning the manganese precipitation supernatant in step C2 for use as a high-concentration ammonium sulfate solution; returning the magnesium precipitation supernatant in step C2 for use as a low-concentration ammonium sulfate solution; and returning the manganese precipitation supernatant in step C1 for use as a first stripping agent.

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