CN114381619A - Method for preparing high-purity mangano-manganic oxide and high-purity magnesium oxide - Google Patents
Method for preparing high-purity mangano-manganic oxide and high-purity magnesium oxide Download PDFInfo
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Abstract
The invention provides a method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide, which comprises the following steps of (1) leaching manganese ore to prepare a manganese-containing solution; (2) carrying out impurity removal treatment; (3) separating manganese and magnesium in the purified liquid by extraction, wherein the manganese enters an organic phase, and the magnesium remains in raffinate; (4) carrying out back extraction on the loaded organic phase by using alkali liquor to obtain a regenerated organic phase and back extraction liquor; (5) filtering the strip liquor to obtain manganese sulfate, and drying to obtain a high-purity manganese sulfate product; (6) adding ammonia water into 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. The method realizes the high-efficiency preparation of the high-purity trimanganese tetroxide by using the alkali back extraction, realizes the high value-added utilization of magnesium, and has the advantages of high resource utilization rate, low cost, environmental protection, cleanness and environmental protection.
Description
Technical Field
The invention relates to the technical field of wet metallurgy, in particular to a method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide.
Background
As an important inorganic functional material, trimanganese tetroxide is widely used in the fields of catalytic active components, electromagnetic materials, electrochemistry, air purification and the like. In recent years, with the development of new energy fields, the demand for power lithium ion batteries has been increasing, and LiMn has been used as LiMn2O4High-quality raw material, high-purity Mn3O4The demand for (a) has also proliferated. At present, Mn3O4The preparation method can be divided into the following methods according to the difference of raw materials: electrolytic manganese metal suspension catalytic oxidation, reduction, roasting, manganese salt hydrothermal oxidation and the like, mainly takes manganese products such as manganese metal, manganese dioxide, manganese sulfate, manganese carbonate and the like as raw materials, and has the problems of high energy consumption, high cost, high impurity content of the products and the like.
Manganese ore is used as a raw material, and the manganese ore leachate is purified to prepare high-purity trimanganese tetroxide, so that energy and reagent consumption can be effectively saved. Chinese patent application CN101049971A discloses a method for preparing high-purity trimanganese tetroxide from pyrolusite as raw material, which comprises soaking pyrolusite in dilute acid, reducing with sulfur dioxide, removing impurities chemically, and oxidizing with air under alkaline condition to obtain high-purity trimanganese tetroxide. Chinese patent application CN110697786A discloses a preparation method of trimanganese tetroxide, which takes manganese carbonate ore as a raw material and prepares high-purity trimanganese tetroxide through the processes of leaching, neutralization, heavy metal removal, calcium and magnesium removal, purification, hydrolysis precipitation and oxidation.
Because the manganese ore in China is mainly low-grade ore and the manganese ore is directly used for preparing the trimanganese tetroxide, the defects of low purity, poor quality stability and the like of the trimanganese tetroxide still exist. On the other hand, the existing precipitation impurity removal process can effectively remove heavy metal ions, but cannot remove magnesium ions, so that the quality of trimanganese tetroxide is influenced, and the waste of magnesium resources is caused. Therefore, a new environment-friendly and economic process is urgently needed to solve the problems of high energy consumption, poor quality stability and unreasonable utilization of associated resources in the existing production method of high-purity trimanganese tetroxide.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide.
In order to achieve the above objects, embodiments of the present invention provide a method of preparing high-purity trimanganese tetroxide and high-purity magnesium oxide, the method including the steps of:
s1: crushing manganese ores, continuously leaching with an acid solution to obtain leaching slag and leaching liquid, and filtering;
s2: adding an oxidant into the leachate for oxidation, adding alkali, adjusting the pH value of the leachate to 4-6, precipitating, adding SDD to remove heavy metal impurities, and filtering to obtain a purified solution and a precipitation slag;
s3: extracting manganese in the purification solution by adopting an organic phase to obtain a loaded organic phase and raffinate, washing the loaded organic phase by using the purification solution to obtain a manganese-rich loaded organic phase and washing solution, and returning the washing solution to the purification solution for circulation;
s4: carrying out back extraction and separation on the manganese-rich loaded organic phase by using an alkaline solution to obtain a back extraction solution and a regenerated organic phase, and returning the regenerated organic phase to the step S3 for recycling;
s5: carrying out solid-liquid separation on the stripping solution, drying to obtain manganous-manganic oxide and filtrate, and returning the filtrate to the step S1 for recycling;
s6: adding an alkaline solution into the raffinate for precipitation, carrying out solid-liquid separation to obtain magnesium hydroxide and an ammonium sulfate solution, and washing and calcining the magnesium hydroxide to obtain magnesium oxide;
s7: evaporating and crystallizing the ammonium sulfate solution to obtain ammonium sulfate and an evaporated solution;
the purity of the manganous-manganic oxide is 70.50 to 71.34 percent (calculated by Mn), d502.86-9.97 μm;
the purity of the magnesium oxide is 99.51-99.85% (calculated by MgO), and the bulk density is 0.406-0.435 g/cm3。
Further, the organic phase consists of an extracting agent saponified by a saponifying agent and a diluent, and the concentration of the extracting agent in the organic phase is 50-500 g/L; the extractant is at least one of alpha-hydroxy-2-ethylhexyl phosphinic acid, alpha-hydroxy-2-ethyl-2-hexene phosphinic acid, n-decanoic acid or neodecanoic acid, and the saponification rate of the extractant is 5-50%; the diluent is sulfonated kerosene, aviation kerosene, No. 260 solvent oil, Escaid110 and C8～C13The saponifier is at least one of sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, ammonia water, ammonium carbonate solution, ammonium bicarbonate solution and magnesium hydroxide suspension, and the concentration of the saponifier is 20-30%.
Further, the acidic solution is sulfuric acid and/or the filtrate obtained in the step S5, the liquid-solid volume-mass ratio of the acidic solution to the manganese ore is 1.2-5: 1, and the use amount of the sulfuric acid is 188-620 kg/t of raw ore; the pH value of the leaching solution is 1-7.
Further, in the step S2, the oxidant is manganese dioxide and/or hydrogen peroxide, and the alkali is at least one of manganese carbonate ore, manganese carbonate, magnesium carbonate, calcium oxide, manganese monoxide, magnesium oxide, sodium hydroxide, and potassium hydroxide.
Further, the extraction is multi-stage countercurrent extraction, the stage number of the multi-stage countercurrent extraction is 2-10, and the volume ratio (O: A) of the organic phase to the water phase is 1-6: 1.
Further, the back extraction is multi-stage counter-current back extraction, the stage number of the multi-stage counter-current back extraction is 1-5, and the volume ratio (O: A) of the organic phase to the water phase is 1-5: 1.
Further, the calcining temperature is 500-1000 ℃.
Further, in the step S4, the alkaline solution is at least one of a sodium hydroxide solution, an ammonia water, a potassium hydroxide solution, and a lithium hydroxide solution, and the concentration of the alkaline solution is 0.5 to 2 mol/L.
Further, the pH value of the purifying liquid is 3-7.
Further, the alkaline solution in step S6 is ammonia and/or the evaporated solution in step S7.
The method comprises the steps of obtaining a solution containing manganese sulfate and magnesium sulfate through leaching and impurity removal processes; obtaining a manganese-loaded organic phase and a magnesium-containing raffinate through extraction, thereby realizing the efficient separation of manganese and magnesium; carrying out back extraction on the loaded organic phase by alkali liquor to directly obtain a regenerated organic phase and manganous-manganic oxide; and precipitating the raffinate with alkali liquor to obtain magnesium hydroxide precipitate, washing the magnesium hydroxide, and calcining to obtain the high-purity magnesium oxide product.
The specific reaction principle of the scheme is as follows:
manganese ores generally contain impurities such as iron, copper, aluminum, nickel, and lead in addition to manganese and magnesium. And (2) carrying out continuous countercurrent leaching on the manganese ore by using an acid solution, wherein manganese carbonate and magnesium carbonate in the manganese ore react with acid and enter the solution in the form of manganese ions and magnesium ions, and simultaneously impurity metals enter the solution in the form of ions to obtain leachate and leaching slag.
The iron in the leaching solution is generally Fe2+It is required to oxidize it to Fe using an oxidizing agent3+Adding alkali to adjust the pH of the solution to 5-6 to remove Fe impurity3+And Al3+The precipitation was complete. After iron and aluminum ions are precipitated, adding an SDD chelating agent, and precipitating heavy metal ions such as lead, copper, nickel and the like through chelation; in the impurity removal process, low-valence iron ions generate high-valence (+ 3-valence) iron ions under the action of an oxidant, aluminum ions and the high-valence iron ions react with alkali to generate hydroxide precipitates, and heavy metal ions such as lead, copper and nickel and the like and an SDD chelating agent generate chelation to generate chelated precipitates; removing impurities, performing solid-liquid separation to obtain purified solution, and purifying to obtain purified solution rich in manganese ions and magnesium ionsThe manganese ion content is 20-50 g/L, the magnesium ion content is 1-10 g/L, and the concentration of impurity ions such as iron, aluminum, nickel, copper, lead and the like is lower than 1 mg/L;
extracting manganese in the purification solution by adopting an organic phase to obtain a loaded organic phase and raffinate, wherein the loaded organic phase is rich in manganese and impurity magnesium, washing the loaded organic phase by using the purification solution to remove the impurity magnesium attached to the organic phase to obtain the manganese-rich loaded organic phase and the purification solution, and the purification solution used for washing can be directly returned to the purification solution for circulation;
in the back extraction process, an alkaline solution is used as a water phase to back extract the manganese-rich loaded organic phase, manganese ions are separated from the organic phase to generate a water phase containing manganous-manganic oxide precipitate and a regenerated organic phase, the water phase containing the manganous-manganic oxide precipitate is subjected to solid-liquid separation to obtain high-purity manganous-manganic oxide and filtrate, the filtrate is returned to the step S1 for reuse, and the regenerated organic phase can be recycled for the extraction process; directly performing back extraction by using alkaline solution aiming at the manganese-loaded organic phase, wherein OH in alkali is mainly used-The acidic extractant complexed with manganese is replaced to generate manganese hydroxide precipitate, the manganese hydroxide is oxidized by air to generate manganomanganic oxide, and meanwhile, the acidic extractant is complexed with cations in alkali liquor to realize regeneration, so that the purpose of saponifying the extractant is achieved, and the organic phase is recycled;
adding an ammonia water solution into the raffinate for precipitation, carrying out solid-liquid separation to obtain a magnesium hydroxide solution and an ammonium sulfate solution, washing the magnesium hydroxide, and calcining to obtain a high-purity magnesium oxide product; magnesium ions in solution and OH in alkaline solution-Reacting magnesium hydroxide precipitate, enabling ammonium sulfate to exist in the solution, realizing the separation of the magnesium hydroxide precipitate and the ammonium sulfate solution through solid-liquid separation, then washing the magnesium hydroxide precipitate by using pure water, decomposing the magnesium hydroxide into magnesium oxide and water under the high-temperature condition, adding sulfuric acid into the ammonium sulfate solution to adjust the magnesium hydroxide solution to be neutral, and obtaining an ammonium sulfate product and a mother solution through evaporative crystallization.
In step S1, if the manganese ore is a manganese oxide ore, a wet reduction leaching process is required, and the reducing agent is at least one of sulfur dioxide, iron sulfide, ferrous sulfide, iron, oxalic acid, hydrogen peroxide, phenols, aromatic amines, methanol, glucose and other sugar organic substances; if the manganese ore is other manganese ores such as manganese carbonate ore and the like, the manganese ore can be directly leached by an acid solution.
In step S2, the oxidant is at least one of manganese dioxide, hydrogen peroxide, sodium chlorate, air, oxygen, and sulfur dioxide, preferably manganese dioxide and/or hydrogen peroxide in order to avoid adding excessive impurities into the leachate, manganese ions generated after the reaction of manganese dioxide can be directly used for producing electrolytic manganese, and water generated after the reaction of hydrogen peroxide can be used for circulating in and out, and no other impurities are generated; the addition amount of the oxidant is 1.0-1.2 times of the theoretical molar amount in the reaction process; the alkali is at least one of manganese carbonate ore, manganese carbonate, magnesium carbonate, calcium oxide, manganese monoxide, magnesium oxide, sodium hydroxide and potassium hydroxide, and the pH of the purified liquid obtained after reaction is 1-7.
And (4) introducing air for oxidation when the manganese hydroxide precipitate in the back extraction solution in the step S5 is not completely oxidized, carrying out solid-liquid separation, washing and drying the precipitate to obtain high-purity trimanganese tetroxide, and returning the filtrate to the step S1 for recycling.
And S6, adding ammonia water to adjust the pH value of the raffinate to about 10%, uniformly stirring, standing, precipitating, performing solid-liquid separation to obtain magnesium hydroxide precipitate and ammonium sulfate solution, washing the magnesium hydroxide precipitate with pure water, drying, and calcining to obtain a high-purity magnesium oxide product, wherein the calcining temperature is 500-1000 ℃.
And step S7, adding sulfuric acid to adjust the pH value to be about 7, evaporating by using an evaporation system to obtain ammonium sulfate crystals and mother liquor, drying the ammonium sulfate crystals at 150 ℃ for 3 hours to obtain an ammonium sulfate product, and returning the mother liquor to the evaporation system for recycling.
The high-efficiency separation of manganese and magnesium is completed through extraction, and the high-efficiency recycling of two metal resources in the manganese ore is realized. In addition, the manganous-manganic oxide is directly prepared by reverse extraction of the loaded organic phase with the alkali liquor, the process is simple, energy is saved, the environment is protected, the raffinate is used for preparing high-purity magnesium oxide and ammonium sulfate products, the additional value utilization is high, and the environment is protected.
The scheme of the invention has the following beneficial effects:
(1) the preparation method of the high-purity trimanganese tetroxide and the magnesium oxide introduces extraction and back extraction links, and realizes the direct preparation of the high-purity trimanganese tetroxide by taking manganese ore as the raw material and the co-production of high-purity magnesium oxide and ammonium sulfate products through the integral production process of leaching, impurity removal, extraction, alkali liquor back extraction and magnesium ammonia recovery from raffinate. The process can simultaneously realize high value-added recovery of two metal resources, achieves the effects of more efficient and clean utilization compared with the conventional manganese ore treatment process, co-produces the ammonium sulfate product to realize the recovery and utilization of ammonia nitrogen wastewater, ensures higher resource utilization rate and product purity, and realizes energy conservation, environmental protection and clean production.
(2) The invention uses alkali liquor back extraction to directly prepare high-purity mangano-manganic oxide, and uses the alkaline solution to directly back extract the manganese-loaded organic phase, and uses OH in the alkali-The acidic extractant complexed with manganese is replaced to generate manganese hydroxide precipitate, the manganese hydroxide is oxidized by air to generate manganomanganic oxide, and meanwhile, the acidic extractant is complexed with cations in alkali liquor to realize regeneration, so that the purpose of saponifying the extractant is achieved, and the organic phase is recycled. The invention avoids the complex preparation operations of acid-adding back extraction, alkali-adding neutralization and precipitation, air high-temperature oxidation and the like in the traditional back extraction process, reduces the operation steps, saves the reagent consumption and energy consumption, and has the advantages of simple process, low cost, energy conservation and environmental protection.
(3) The alpha-hydroxy-2-ethylhexyl phosphinic acid and alpha-hydroxy-2-ethyl-2-hexenylphosphinic acid extracting agent used in the invention has two functional groups of phosphinic acid group and hydroxyl group in the molecular structure, and also contains factors such as branched chain structure, steric hindrance effect in the molecule, association between molecules and the like, so that the extracting agent has better binding capacity, higher selectivity and stability compared with the traditional extracting agent. Meanwhile, the organic phosphonic acid extractant and the capric acid extractant are cooperatively extracted, so that the extraction dynamic performance of the extractant can be improved, the phase separation in the extraction process is quicker, the time consumption is shorter, and the energy is saved and the efficiency is higher.
(4) The preparation method of high-purity trimanganese tetroxide and magnesium oxide provided by the invention takes the original manganese ore as the raw material, and compared with the traditional method which takes manganese products such as metal manganese, manganese dioxide, manganese sulfate, manganese carbonate and the like as the raw material, the preparation method can greatly reduce the cost and energy consumption, improve the economic benefit, realize the high-efficiency utilization of low-grade manganese ore in China, and have economic and environmental protection benefits.
Drawings
FIG. 1 is a flow chart of high purity manganomanganic oxide and magnesium oxide prepared by an embodiment of the present invention;
FIG. 2 is a XRD analysis result of high purity trimanganese tetroxide prepared in example 1 of the present invention;
FIG. 3 is a result of particle size analysis of high purity trimanganese tetroxide prepared in example 1 of the present invention;
FIG. 4 is a XRD analysis result of the high purity magnesium oxide prepared in example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Manganese ore used in the following examples of the invention is manganese carbonate ore from Guizhou, the manganese grade is 11.65%, and the magnesium grade is 3.04%; the agents used in the following examples are all commercially available unless otherwise specified.
Aiming at the existing problems, the invention provides a method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide.
As shown in fig. 1, the embodiment of the present invention provides a process flow diagram of a method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide.
Example 1
Production method of electrolytic manganese
The method comprises the working procedures of leaching, impurity removal, extraction, back extraction and ammonia nitrogen and magnesium recovery, and specifically comprises the following steps:
s1, leaching: diluting 18.23g of concentrated sulfuric acid to 95mL by using water, adding 30g of crushed manganese ore powder, stirring and leaching at 90 ℃ for 3h, and filtering to obtain a leaching solution and leaching residues, wherein the pH of the leaching end point is 1.53, the leaching rate of manganese is 96.34%, and the concentration of each element in the leaching solution is as follows: mn 35.44g/L, Mg 9.14.14 g/L, Fe 2.96.96 g/L, Na 0.38.38 g/L, Ca 0.33.33 g/L, Al 0.11.11 g/L;
s2, removing impurities: adding manganese dioxide into the leachate obtained in the step S1 to oxidize low-valent iron, wherein the ratio of the amount of substances added in the manganese dioxide to the amount of substances of the low-valent iron in the leachate is 0.5:1, then adding sodium hydroxide to adjust the pH value to 5.47, precipitating Fe and Al ions, then adding SDD to react to generate chelate precipitate, wherein the addition amount of the SDD is 0.53 kg/ton of raw ore, and filtering to obtain impurity metal precipitate and a purifying solution, wherein the concentrations of all metal ions in the purifying solution are respectively: mn 35.33g/L, Mg 9.11g/L, Fe < 1Mg/L, Al < 1Mg/L, Ni < 1Mg/L, Cu < 1 Mg/L;
and S3, performing secondary countercurrent extraction on the purified liquid obtained in the step S2 and an organic phase with the saponification rate of 30% to obtain a loaded organic phase and raffinate, detecting that the manganese concentration of the organic phase is 9.65g/L and the magnesium concentration is 0.79g/L, washing the loaded organic phase by adopting a manganese sulfate solution at the pH value of 5.0-5.5 to remove magnesium impurities in the loaded organic phase to obtain a manganese-rich loaded organic phase and a washing liquid, and returning the washing liquid to the purified liquid for circulation. Through detection, the manganese concentration in the organic phase is 10.44g/L, and the magnesium concentration is 0.0025 g/L. Wherein the organic phase consists of an extracting agent and a diluent, the extracting agent is alpha-hydroxy-2-ethylhexyl phosphinic acid, the concentration is 300g/L, and the diluent is No. 260 solvent oil; the extractant in the organic phase is firstly saponified by 30 percent ammonia water solution, and the saponification rate is 30 percent; controlling the ratio of O to A to 1.7 to 1 in the process of countercurrent extraction;
and S4, back-extracting the manganese-rich loaded organic phase in the step S3 by using 0.76mol/L ammonia water solution, wherein the ratio of O to A is 2:1, so as to obtain a back-extraction solution and a regenerated organic phase, and separating the back-extraction solution and the regenerated organic phase.
S5, carrying out solid-liquid separation on the stripping solution to obtain a precipitate and a water phase, washing the precipitate for 3 times by using pure water, and drying for 4 hours at 80 ℃ to obtain a high-purity trimanganese tetroxide product with the purity of 70.69%. The XRD analysis result of the prepared high-purity trimanganese tetroxide is shown in figure 2, and the particle size analysis result is shown in figure 3.
S6, adding a small amount of ammonia water into the raffinate (Mg 6.24g/L, Mn 0.34.34 g/L), adjusting the pH of the solution to 7.8, stirring for 10min, and standing for 1h to precipitate the impurity manganese in the solution. Separating impurity manganese by solid-liquid separation to obtain solution containing ammonium sulfate and magnesium sulfate (wherein Mn is 0.003g/L), continuously adding ammonia water into the solution until pH is 10, stirring for 20min, precipitating magnesium in the solution in the form of magnesium hydroxide, standing for 1.5h after stirring is finished, and separating to obtain magnesium hydroxide precipitate and ammonium sulfate solution. Washing the magnesium hydroxide precipitate with pure water for 3 times, drying at 80 ℃ for 4h, and then calcining at 900 ℃ for 2h to obtain a high-purity magnesium oxide product with the purity of 99.51%. The XRD analysis result of the prepared high-purity magnesium oxide is shown in fig. 4.
S7, adding a sulfuric acid solution into the ammonium sulfate solution to adjust the pH of the solution to 7. Evaporating the solution by using an evaporation crystallizer, centrifugally separating out crystals, and returning the separated mother liquor to the system for continuous evaporation, concentration and crystallization. And (4) crystallizing and drying for 4 hours at 120 ℃ to obtain an ammonium sulfate product.
Example 2
Production method of electrolytic manganese
The method comprises the working procedures of leaching, impurity removal, extraction, back extraction and ammonia nitrogen and magnesium recovery, and specifically comprises the following steps:
s1, leaching: diluting 18.19g of concentrated sulfuric acid to 130mL by using water, adding 30g of crushed manganese ore powder, stirring and leaching at 50 ℃ for 5h, and filtering to obtain a leaching solution and leaching residues, wherein the end point pH of the leaching solution is 1.53, the leaching rate of manganese is 97.41%, and the concentrations of elements in the leaching solution are as follows: mn 26.19g/L, Mg 6.83.83 g/L, Fe 2.19.19 g/L, Na 0.28.28 g/L, Ca 0.24.24 g/L, Al 0.08.08 g/L;
s2, removing impurities: adding hydrogen peroxide into the leachate obtained in the step S1 to oxidize low-valent iron, wherein the ratio of the amount of substances added in the hydrogen peroxide to the amount of substances of the low-valent iron in the leachate is 0.5:1, then adding sodium hydroxide to adjust the pH value to 5.26, precipitating Fe and Al ions, then adding SDD to react to generate chelate precipitate, wherein the addition amount of the SDD is 0.53 kg/ton of raw ore, and filtering to obtain impurity metal precipitates and a purifying solution, wherein the concentrations of all metal ions in the purifying solution are respectively: 26.15g/L of Mn, 6.76g/L of Mg, less than 1Mg/L, Al of Fe and less than 1Mg/L of Fe, less than 1Mg/L of Ni and less than 1Mg/L of Cu;
and S3, performing secondary countercurrent extraction on the purified liquid obtained in the step S2 and an organic phase with the saponification rate of 30% to obtain a loaded organic phase and raffinate, detecting that the manganese concentration of the organic phase is 9.74g/L and the magnesium concentration is 0.81g/L, washing the loaded organic phase by adopting a manganese sulfate solution at the pH value of 5.0-5.5 to remove magnesium impurities in the loaded organic phase to obtain a manganese-rich loaded organic phase and a washing liquid, and returning the washing liquid to the purified liquid for circulation. Through detection, the manganese concentration in the organic phase is 10.55g/L, and the magnesium concentration is 0.0026 g/L. Wherein the organic phase consists of an extracting agent and a diluting agent, the extracting agent is alpha-hydroxy-2-ethyl-2-hexenylphosphinic acid, the concentration is 300g/L, and the diluting agent is sulfonated kerosene; the extractant in the organic phase is firstly saponified by 30 percent ammonia water, and the saponification rate is 30 percent; controlling the ratio of O to A to 1.3 to 1 in the process of countercurrent extraction;
and S4, back-extracting the manganese-rich loaded organic phase in the step S3 by using 1.15mol/L ammonia water solution, wherein the ratio of O to A is 3:1 to obtain a back-extraction solution and a regenerated organic phase, and separating the back-extraction solution and the regenerated organic phase.
S5, carrying out solid-liquid separation on the stripping solution to obtain a precipitate and a water phase, washing the precipitate for 4 times by using pure water, and drying for 2 hours at 120 ℃ to obtain a high-purity trimanganese tetroxide product with the purity of 71.34%.
S6, adding a small amount of ammonia water into the raffinate (Mg 4.50g/L, Mn 0.25.25 g/L), adjusting the pH of the solution to 7.7, stirring for 15min, and standing for 1.5h to precipitate the impurity manganese in the solution. Separating manganese impurities by solid-liquid separation to obtain a solution containing ammonium sulfate and magnesium sulfate (wherein Mn is 0.0028g/L), continuously adding ammonia water into the solution until the pH value is 9.5, stirring for 25min, precipitating magnesium in the solution in the form of magnesium hydroxide, standing for 2h after stirring is finished, and separating to obtain the magnesium hydroxide precipitate and the ammonium sulfate solution. Washing the magnesium hydroxide precipitate with pure water for 4 times, drying at 120 ℃ for 2h, and then calcining at 500 ℃ for 3h to obtain a high-purity magnesium oxide product with the purity of 99.85%.
S7, adding a sulfuric acid solution into the ammonium sulfate solution to adjust the pH of the solution to 6.5. Evaporating the solution by using an evaporation crystallizer, centrifugally separating out crystals, and returning the separated mother liquor to the system for continuous evaporation, concentration and crystallization. And (3) crystallizing and drying for 3h at 150 ℃ to obtain an ammonium sulfate product.
Example 3
The method for producing electrolytic manganese in this embodiment is the same as that in embodiment 1, except that, in step S3, neodecanoic acid is used as an extracting agent, aviation kerosene is used as a diluent, the concentration is 400g/L, 30% by mass of sodium hydroxide solution is used for saponification until the saponification rate is 20%, the pH of the purified liquid is adjusted to 4, the ratio of O to a is 1:1 in the countercurrent extraction process, the purified liquid obtained in step S2 and an organic phase with the saponification rate of 20% are subjected to secondary countercurrent extraction to obtain a loaded organic phase and raffinate, the manganese concentration in the loaded organic phase is detected to be 8.79g/L, the magnesium concentration is 0.73g/L, the loaded organic phase is washed with a manganese sulfate solution at pH 5.0-5.5, the magnesium impurity in the loaded organic phase is removed, the manganese-rich loaded organic phase and the wash liquid are returned to the purified liquid for circulation. Through detection, the manganese concentration in the organic phase is 9.52g/L, and the magnesium concentration is 0.0023 g/L.
Example 4
The method for producing electrolytic manganese in this example is the same as that of example 1, except that in step S3, neodecanoic acid and α -hydroxy-2-ethyl-2-hexenylphosphinic acid are used as co-extractants, Escaid110 is used as a diluent, and the concentration of the extractant is 300g/L, wherein the concentration of neodecanoic acid is 150g/L, the concentration of α -hydroxy-2-ethyl-2-hexenylphosphinic acid is 150g/L, 30% by mass of sodium hydroxide solution is used for saponification, the saponification rate is 30%, the pH of the purified solution is adjusted to 5, in the countercurrent extraction process, O: a is controlled to be 1.7:1, the purified solution obtained in step S2 and an organic phase with the saponification rate of 30% are subjected to two-stage countercurrent extraction to obtain a loaded organic phase and a raffinate, and the detected organic phase has a manganese concentration of 9.76g/L, a magnesium concentration of 0.81g/L, and washing the loaded organic phase by adopting a manganese sulfate solution at the pH value of 5.0-5.5 to remove impurity magnesium in the loaded organic phase to obtain the manganese-rich loaded organic phase and a washing solution, and returning the washing solution to the purified solution for circulation. Through detection, the manganese concentration in the organic phase is 10.58g/L, and the magnesium concentration in the organic phase is 0.0026 g/L. In the experimental process, compared with a single extracting agent, the neodecanoic acid in the synergistic extracting agent has better performance on extraction kinetics, higher extraction speed and fast phase separation by adding the neodecanoic acid, and the existence of two functional groups, namely a phosphinic acid group and a hydroxyl group in alpha-hydroxy-2-ethyl-2-hexenylphosphinic acid enables the alpha-hydroxy-2-ethyl-2-hexenylphosphinic acid to have better binding capacity and stability.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing high purity trimanganese tetroxide and high purity magnesium oxide, comprising the steps of:
s1: crushing manganese ores, continuously leaching with an acid solution to obtain leaching slag and leaching liquid, and filtering;
s2: adding an oxidant into the leachate for oxidation, adding alkali, adjusting the pH value of the leachate to 4-6, precipitating, adding SDD to remove heavy metal impurities, and filtering to obtain a purified solution and a precipitation slag;
s3: extracting manganese in the purification solution by adopting an organic phase to obtain a loaded organic phase and raffinate, washing the loaded organic phase by using the purification solution to obtain a manganese-rich loaded organic phase and washing solution, and returning the washing solution to the purification solution for circulation;
s4: carrying out back extraction and separation on the manganese-rich loaded organic phase by using an alkaline solution to obtain a back extraction solution and a regenerated organic phase, and returning the regenerated organic phase to the step S3 for recycling;
s5: carrying out solid-liquid separation on the stripping solution, drying to obtain manganous-manganic oxide and filtrate, and returning the filtrate to the step S1 for recycling;
s6: adding an alkaline solution into the raffinate for precipitation, carrying out solid-liquid separation to obtain magnesium hydroxide and an ammonium sulfate solution, and washing and calcining the magnesium hydroxide to obtain magnesium oxide;
s7: evaporating and crystallizing the ammonium sulfate solution to obtain ammonium sulfate and an evaporated solution;
the purity of the manganous-manganic oxide is 70.50 to 71.34 percent (calculated by Mn), d502.86-9.97 μm;
the purity of the magnesium oxide is 99.51-99.85% (calculated by MgO), and the bulk density is 0.406-0.435 g/cm3。
2. The method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide according to claim 1, wherein the organic phase is composed of an extractant saponified by a saponifying agent and a diluent, and the concentration of the extractant in the organic phase is 50-500 g/L; the extractant is at least one of alpha-hydroxy-2-ethylhexyl phosphinic acid, alpha-hydroxy-2-ethyl-2-hexene phosphinic acid, n-decanoic acid or neodecanoic acid, and the saponification rate of the extractant is 5-50%; the diluent is sulfonated kerosene, aviation kerosene, No. 260 solvent oil, Escaid110 and C8～C13The saponifier is at least one of sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, ammonia water, ammonium carbonate solution, ammonium bicarbonate solution and magnesium hydroxide suspension, and the concentration of the saponifier is 20-30%.
3. The method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide according to claim 1, wherein the acidic solution is sulfuric acid and/or the filtrate obtained in the step S5, the liquid-solid volume-mass ratio of the acidic solution to the manganese ore is 1.2-5: 1, and the amount of the sulfuric acid is 188-620 kg/t of raw ore; the pH value of the leaching solution is 1-7.
4. The method of claim 1, wherein the oxidant in step S2 is manganese dioxide and/or hydrogen peroxide, and the alkali is at least one of manganese carbonate ore, manganese carbonate, magnesium carbonate, calcium oxide, manganese monoxide, magnesium oxide, sodium hydroxide, and potassium hydroxide.
5. The method for preparing high-purity manganous-manganic oxide and high-purity magnesium oxide according to claim 1, wherein the extraction is multi-stage countercurrent extraction, the number of stages of the multi-stage countercurrent extraction is 2-10, and the volume ratio of the organic phase to the aqueous phase is 1-6: 1.
6. The method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide according to claim 1, wherein the back extraction is multi-stage counter-current back extraction, the number of stages of the multi-stage counter-current back extraction is 1-5, and the volume ratio of the organic phase to the aqueous phase is 1-5: 1.
7. The method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide according to claim 1, wherein the calcination temperature is 500-1000 ℃.
8. The method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide according to claim 1, wherein the alkaline solution in step S4 is at least one of sodium hydroxide solution, ammonia water, potassium hydroxide solution and lithium hydroxide solution, and the concentration of the alkaline solution is 0.5-2 mol/L.
9. The method for preparing high-purity trimanganese tetroxide and high-purity magnesium oxide according to claim 1, wherein the pH of the purified liquid is 3-7.
10. The method for preparing high purity trimanganese tetroxide and high purity magnesium oxide according to claim 1, wherein the alkaline solution in step S6 is ammonia and/or the evaporated solution in step S7.
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