291results about "Manganese sulfates" patented technology

The invention discloses a method for preparing high-purity manganese sulfate and co-producing manganese dioxide for a battery by reducing manganese oxide ore with sulfur dioxide, metal smelting SO2-containing flue gas or sulfur acid-making industry SO2 gas is used as a reducing agent, discharged tail gas after absorption can be as low as 30 mg / m < 3 > or below, and the leaching rate of manganese element can reach 98% or above. By adopting the technical scheme of the process, the comprehensive recovery rate of manganese is easy to achieve more than 95%, and two high-value products of high-purity MnSO4 and MnO2 for batteries are produced; s2O6 < 2-> is decomposed and removed in the same reaction kettle by adopting a high-temperature oxidation process to obtain a manganese sulfate solution and co-produce a high-quality MnO2 product suitable for batteries; a speed-controlled crystallization method is adopted for high-temperature crystallization, the one-time crystallization separation and purification rate of impurity ions such as magnesium, calcium, potassium and sodium is stably increased from 70-80% to 90% or above, and the purpose of obtaining a battery-grade high-purity manganese sulfate product through two times of recrystallization is achieved.

The invention discloses a method for recovering and separating nickel, cobalt and manganese from waste ternary lithium ion battery material lithium extraction slag, which comprises the following steps: pulping waste ternary battery material lithium extraction slag, leaching, introducing compressed air as an oxidant, and carrying out solid-liquid separation after leaching to obtain a leachate and leaching slag; sequentially performing copper removal, iron removal, aluminum removal and fluorine removal on the leachate to finally obtain fluorine-removed liquid; carrying out refined filtration on the fluorine-removed liquid to obtain a refined-filtered liquid; adjusting the pH value of the finely filtered liquid, and extracting impurities by using nickel soap P204 to obtain a rich organic phase and raffinate 1; extracting manganese from the raffinate 1 by using nickel soap P204 to obtain a manganese-rich organic phase and raffinate 2; extracting cobalt from the raffinate 2 by using nickel soap P507 to obtain a cobalt-rich organic phase and raffinate 3; and carrying out evaporative crystallization on the raffinate 3 to obtain nickel sulfate. The whole process has the advantages of short flow, high metal recovery rate, high product quality and low sodium-containing wastewater treatment capacity, and nickel, cobalt, manganese and lithium elements in the waste ternary lithium ion battery material are efficiently recycled by combining a front-end lithium extraction and recovery process, so that resource circulation is realized.

A treatment process for crystallizing a metal sulfate involving pre-treating a feedstock comprising calcium, magnesium, and / or lithium impurities, the pre-treating involving pre-leaching the feedstock in the presence of a lixiviant, selectively extracting a first portion of any of the impurities from the feedstock, and forming a leached solution comprising an uncrystallized metal sulfate and any remaining impurities; and / or refining the leached solution and removing a second portion of any of the remaining impurities; and crystallizing the uncrystallized metal sulfate from the leached solution to form a crystallized metal sulfate. So processed, the crystallized metal sulfate may be battery-grade or electroplating-grade.

The invention belongs to the field of lithium recovery, and particularly relates to a method and a system for electrochemically recovering lithium ions in ternary lithium battery leachate. The method comprises the following steps: (1) leaching the cathode material of the waste ternary battery to obtain a ternary leachate; (2) performing lithium ion enrichment in a capacitive deionization device by taking the ternary leaching solution obtained in the step (1) as a lithium source to obtain a lithium-rich receiving solution and a lithium-removed recycling solution; (3) recovering the lithium-rich receiving liquid to obtain recovered lithium; and performing non-lithium metal element recovery on the lithium-removed recovery liquid. According to the technical scheme, the rocking chair type capacitive deionization RCDI system adopts a waste ternary battery cathode material (SNCM) as an electrode material, the extraction quantity of a single reaction cycle can reach 4.90 mM g <-1 >, continuous and selective lithium extraction is realized, and meanwhile, the cost and the environmental influence are reduced.

The invention provides a method for preparing high-purity manganese sulfate by taking pyrolusite and pyrite as raw materials, which comprises the following steps: carrying out reduction reaction on the pyrolusite and the pyrite by adopting acid leaching to obtain a manganese sulfate solution, and continuously feeding the pyrolusite until ferrous ions in the system are completely oxidized into iron ions; adding a pH regulator to remove iron, adding a vulcanizing agent to remove heavy metals, adding a pH regulator to remove silicon and aluminum, and carrying out solid-liquid separation to obtain a manganese sulfate solution containing calcium and magnesium; adding a fluorinating agent into the manganese sulfate solution containing calcium and magnesium to remove calcium and magnesium, and carrying out solid-liquid separation to obtain a fluorine-containing high-purity manganese sulfate solution; and extracting the fluorine-containing high-purity manganese sulfate solution to obtain a fluorine-containing organic phase and battery-grade high-purity manganese sulfate. According to the method, the medicament cost in the removal process is greatly reduced, namely, the raw material pyrolusite is used for replacing an external oxidant to oxidize Fe < 2 + > in a system, and a large amount of jarosite and sodium jarosite are generated in situ, so that complete removal of potassium, sodium and iron is realized.

The invention belongs to the technical field of waste battery recovery and regeneration, and particularly relates to a method for recovering valuable metal from a waste lithium battery positive electrode material. The method comprises the following steps: carrying out sulfuration roasting on waste positive electrode powder, selectively extracting lithium in a water leaching manner, and precipitating lithium to obtain lithium carbonate; separating and purifying the nickel, the cobalt and the manganese through microwave acid leaching, precipitation impurity removal and step-by-step extraction to obtain extract liquor of the nickel, the cobalt and the manganese, and performing reverse extraction on the extract liquor to obtain battery-grade cobalt sulfate, battery-grade nickel sulfate and battery-grade manganese sulfate. According to the method, lithium is extracted firstly, the influence of the lithium element on subsequent nickel-cobalt-manganese extraction is reduced, meanwhile, the recovery rate of lithium is increased through the water leaching method, and the recovery cost is reduced. According to the method, precipitation and impurity removal are performed before nickel-cobalt-manganese extraction, so that the content of impurities in a sulfate solution is reduced, and the recovery rate of nickel, cobalt and manganese is greatly improved.

The invention belongs to the technical field of new energy materials, and discloses a sodium manganese sulfate sulfuration impurity removal method, which is divided into two stages of sulfuration, the first stage is that sodium sulfide reacts with manganese sulfate, the pH value is controlled to be 5-6, the second stage is that a small amount of sodium sulfide is added for continuous sulfuration, the pH value is controlled to be stabilized at 6.4-7.0, and the content of calcium, magnesium and other impurities in manganese sulfate is reduced as much as possible through secondary sulfuration. And the generated manganese sulfide is treated in the later stage to obtain manganese sulfate with low content of impurities such as calcium and magnesium. The quality of the refined manganese sulfate solution is improved by using a simple process, the impurity content is reduced, and the quality stability of the manganese sulfate product is improved, so that the market competitiveness of the high-purity manganese sulfate product is improved.

The utility model discloses a production line for preparing manganese sulfate from zinc smelting manganese-containing slag, the production line for preparing manganese sulfate from zinc smelting manganese-containing slag comprises an autoclave evaporator and at least one reaction tank, the autoclave is provided with a gas inlet and a gas outlet opposite to the gas inlet, the autoclave is suitable for accommodating a zinc anode slime mixture, the gas inlet is suitable for introducing reducing gas, and the gas outlet is suitable for introducing reducing gas; carrying out reduction leaching reaction with a zinc anode mud mixture; the reaction tank is positioned at the downstream of the high-pressure kettle and is used for performing impurity removal treatment on a solution flowing into the reaction tank; and the evaporator is positioned at the downstream of the reaction tank and is suitable for evaporating, crystallizing and drying the solution flowing into the evaporator. Therefore, through the cooperation of the autoclave, the reaction tank and the evaporator, a continuous production line for reduction leaching, purification and impurity removal, evaporative crystallization and drying is formed, the high value of manganese ions and the recycling of the zinc smelting manganese-containing slag can be optimized, the technological process and the production cost can be saved, and the production line is high in applicability and universality, environmentally friendly and capable of saving energy.

The invention discloses a method for preparing a manganese sulfate crystal by using manganese carbonate ore. The preparation method of the manganese sulfate crystal comprises the following steps: leaching manganese carbonate ore by using sulfuric acid to obtain a leaching solution, precipitating the leaching solution by using a heavy removing agent to remove heavy metal ions, neutralizing redundant sulfuric acid in the leaching solution, introducing a precipitating agent, reacting with the precipitating agent to obtain a precipitate, washing the precipitate with water to remove impurities, and dissolving by using sulfuric acid to obtain the manganese sulfate crystal. And after dissolving, precipitating a small amount of residual calcium and magnesium ions by using fluoride, filtering to obtain fluorine-containing manganese sulfate filtrate, finally adding a fluorine removal agent for solid-liquid separation, and evaporating and crystallizing the filtrate to obtain manganese sulfate crystals. The manganese sulfate crystal is suitable for production of a lithium ion battery positive electrode material. According to the preparation method of the manganese sulfate crystal, the impurity removal cost is greatly reduced. The invention also discloses a method for preparing manganous-manganic oxide from manganese carbonate ore. The tap density of the manganous-manganic oxide is greater than 2.3 g / cm < 3 >, the specific surface area is less than 3m < 2 > / g, and the requirement of a battery-grade material is met.

The present application relates to electrolytic manganese technology field, specifically to a kind of method for removing heavy metal ions in manganese sulfate solution.The method for removing heavy metal ions in manganese sulfate solution provided by the present application includes the following steps: adding oxidizing agent to pretreated manganese sulfate solution, mixing and stirring, then adjusting the pH value of solution to 5.5-6.0, filtering, to obtain the first purified manganese sulfate solution;Add sulfidation agent to the first purified manganese sulfate solution, filter, to obtain the second purified manganese sulfate solution;Add porous resin polymer to the second purified manganese sulfate solution, add the mixed solution into a sealed container, introduce nitrogen, make the pressure in the sealed container reach 1.1-1.5MPa and maintain for 2-10min, then open the air valve and release pressure instantaneously, stand, filter, fine filter, to obtain the purified manganese sulfate solution.The method provided by the present application can not only effectively remove heavy metal ions in solution, but also effectively reduce the COD value of the purified solution, reduce the loss of manganese content in solution.

The invention provides a manganese sulfate purification method based on a membrane separation technology, and relates to the technical field of manganese sulfate purification, the manganese sulfate purification method comprises the following steps: S1, pretreatment and solution blending: starting a stirring tank for stirring at a stirring speed of 230-500 RPM; adding a raw material solution into the stirring tank; adding a mixed solvent into the raw material solution, wherein the total adding amount of the mixed solvent accounts for 1-2% of the mass of the raw material solution; according to the preparation method, a mixed solvent and a stability additive are introduced in the raw material solution preparation stage, and the stirring speed and the reaction temperature are regulated and controlled, so that the uniformity and the system stability of raw material components are enhanced, the solubility and the dispersity of impurity components are reduced, and subsequent impurities are promoted to be thoroughly and sufficiently settled; in the chemical precipitation stage, precipitation of the impurities is accelerated by controlling the proportion of a precipitator, the reaction temperature and the stirring speed, so that the precipitation rate and the particle size uniformity of precipitated particles are improved, and the impurities are fully separated from a main solution.

The invention discloses an all-component waste lithium ion battery recycling method based on residual energy driving. The method comprises the following steps: placing the waste lithium ion battery containing residual electric quantity in a closed environment filled with inert gas, inducing the battery to generate internal short circuit, converting the residual electric quantity into heat, and further triggering a diaphragm and electrolyte to be heated and decomposed to obtain an internal short circuit product; crushing and screening the internal short-circuit product to obtain an undersize product which is black powder No.1 and an oversize product which is a current collector foil; leaching the black powder No.1 by using a leaching agent to obtain slurry; and carrying out wet magnetic separation on the slurry to separate out metal powder, wherein the remainder is a mixture of black powder No.2 and a lithium-containing leachate. According to the method, the recovery process of the waste battery is simplified, the residual energy of the battery is fully utilized, the energy utilization rate and the recovery efficiency are improved, energy loss hardly exists, and the method has remarkable economic benefits and environmental protection benefits.

The invention provides a method for recycling battery-grade manganese sulfate from manganese-containing feed liquid. The method comprises the following steps: (1) carrying out resin adsorption on a manganese-containing feed liquid to obtain a nickel-cobalt adsorbate and an adsorbed feed liquid; (2) sequentially carrying out extraction treatment and reverse extraction treatment on the adsorbed feed liquid to obtain a solution containing manganese sulfate and an organic phase after reverse extraction; (3) carrying out evaporative crystallization on the solution containing manganese sulfate to obtain battery-grade manganese sulfate; positive ions in the manganese-containing feed liquid comprise manganese ions, nickel ions, cobalt ions, calcium ions and magnesium ions, and negative ions in the manganese-containing feed liquid comprise sulfate ions; an extraction agent adopted in the extraction treatment process comprises an HBL116 extraction agent. According to the method disclosed by the invention, metal oxidation hydrolysis cannot be caused to generate a third phase, the extraction process is stable, enrichment of a high-concentration manganese sulfate solution is realized, high-purity manganese sulfate crystals with qualified impurities are obtained, and efficient recovery of manganese in a high-calcium-magnesium feed liquid system can be realized; and a complicated recovery process is not needed, so that the cost is lower.

The invention provides a preparation method for low-carbon environment-friendly linkage production of high-purity manganese sulfate, which comprises the following steps of: mixing mineral powder into pulp, desulfurizing and extracting manganese, adding an impurity removing agent into the obtained manganese sulfate crude liquid, carrying out filter pressing to obtain manganese sulfate fine filtrate, evaporating, concentrating and concentrating to obtain manganese sulfate concentrated liquid, adding concentrated sulfuric acid, and crystallizing twice to obtain high-purity manganese sulfate. Primary crystals, primary crystallization mother liquor, secondary crystals and secondary crystallization mother liquor are obtained respectively; adding water into the crystals, pulping, neutralizing and drying to obtain the high-purity manganese sulfate. According to the method, a manganese sulfate solution is produced through wet reduction of sulfur dioxide, high-purity manganese sulfate is obtained through purification and impurity reduction through acidification and crystallization of concentrated sulfuric acid, primary crystallization mother liquor, secondary crystallization mother liquor and rhodochrosite are chemically combined, and the mixture is directly transferred to a production line for producing EMD, manganese metal, industrial-grade manganese sulfate or feed-grade manganese sulfate to be used for producing manganese-containing compounds.

The present disclosure provides a method of recovering a spent battery cathode material comprising lithium and at least one of nickel, cobalt and / or manganese, the method comprising: heating the spent battery cathode material in a reducing atmosphere to form a heat-treated spent battery cathode material comprising LiF and one or more of LijO, LiOH and LijCOs; washing the heat treated waste battery cathode material in an aqueous solvent to extract lithium-containing species and fluorine-containing species wherein the aqueous solvent is free of alkaline earth metal hydroxides or other species intended to reduce or prevent soluble fluorine species from remaining dissolved in the aqueous solvent; separating an aqueous solvent comprising lithium and fluorine species from the heat treated waste battery material; after separating an aqueous solvent comprising lithium and fluorine species from the heat-treated waste battery material, treating the aqueous solvent to separate lithium species from fluorine species; recycling a lithium substance in the form of lithium hydroxide or lithium carbonate; forming an acidic aqueous recovery feed comprising one or more of nickel, cobalt and / or manganese by leaching the heat treated waste battery cathode material with a mineral acid after the step of separating the aqueous solvent from the heat treated waste battery material; and recovering one or more of nickel, cobalt and / or manganese from the acidic aqueous recovery feed by a further process step selected from one or more of solvent extraction, solid phase extraction, electrochemical extraction and precipitation processes.

A waste battery processing method includes a discharging process of discharging a waste battery, a dismantling process of dismantling the discharged waste battery into battery cell units, a shredding process of shredding the dismantled waste battery, a roasting process of roasting the shredded waste battery, a pulverizing process of pulverizing the fired waste battery, and a hydrometallurgical process of extracting and recovering metals from the pulverized waste battery.

The invention discloses a cyclic utilization method of electrolytic manganese ammonium sulfate double salt. The method comprises the steps that S1, crushed manganese mineral powder is fed into a calcining furnace to be calcined under shielding gas, the typical calcining temperature ranges from 600 DEG C to 700 DEG C, the calcining time ranges from 0.5 h to 5 h, and the main reaction carried out in the calcining furnace is MnCO3 = MnO + CO2 (gas); s2, ammonium sulfate double salt is preheated and dewatered through CO2 released by the calcinator, then the dewatered ammonium sulfate double salt enters the calcinator, the ammonium sulfate double salt and manganese mineral powder are mixed and roasted under the protection of shielding gas, the typical roasting temperature can be 500 DEG C, the roasting time is 1-10 hours, and the main reaction carried out in the calcinator is MnO + (NH4) 2SO4 = MnSO4 + 2NH3 superscript + H2O superscript. According to the cyclic utilization method of the electrolytic manganese ammonium sulfate double salt, the manganese mineral powder is activated by using the ammonium sulfate double salt, so that the reuse of sulfate radicals is realized, and the requirement on sulfuric acid in the leaching process is obviously reduced.

The invention belongs to the technical field of waste battery recovery, and particularly relates to a short-process method for recovering battery-grade lithium carbonate and valuable metals from waste ternary lithium battery black powder. According to the method, a lithium closed-loop technical system of blank roasting, cyclic leaching, synergistic impurity removal, lithium phosphate aluminum removal, directional extraction and split-flow extraction of lithium, nickel and magnesium and seed crystal induction parallel flow lithium precipitation is constructed, a roasting aid, a reducing agent and an aluminum removal agent do not need to be added in the whole process, and the redundant processes of traditional lithium carbonate purification such as carbonization, resin purification and pyrolysis are omitted; the lithium liquid concentration cost is saved, no hazardous waste exists, green and clean production is achieved, and the quality of battery-grade products is guaranteed through collaborative impurity removal and directional extraction.

The invention provides a method for extracting and producing battery-grade manganese sulfate, which comprises the following steps: by taking ferrous sulfate as a reducing agent, leaching low-grade manganese oxide ore by using a sulfuric acid solution, then removing iron ions and heavy metal ions through barium sulfide precipitation, and finally extracting by using alpha-hydroxyalkylphosphinic acid to extract manganese sulfate into an organic phase and magnesium, zinc and the like into a water phase, thereby obtaining the battery-grade manganese sulfate. Therefore, the effect of improving the purity of manganese sulfate is achieved, and finally high-purity manganese sulfate is prepared. According to the method, after the manganese ore is reduced and leached by adopting the leached ferrous sulfate, iron ion impurities are removed by adopting barium sulfide precipitation, and impurities such as magnesium and zinc are further removed through extraction, so that the purity of the manganese sulfate in an organic phase is greatly improved, and a technical direction is provided for producing the high-purity manganese sulfate.

The invention discloses a green continuous production process of electrolytic manganese dioxide, which comprises the following steps: mixing a manganese-containing raw material and sulfuric acid according to a mass ratio of 1: (1.2-1.5), and then carrying out acid leaching at 80-90 DEG C for 2-3 hours to improve the manganese leaching rate to 91-98%; 10-15% hydrogen peroxide oxidation is combined with accurate regulation and control and flocculent precipitation of pH 5-6, so that the iron impurity residue is less than or equal to 5 ppm; in the electrolysis process, sulfuric acid is continuously supplemented to maintain the concentration of 150-180 g / L, the titanium-based lead dioxide anode and the stainless steel cathode are matched, and the current efficiency is 88-91.5%; and carrying out three-stage countercurrent washing and drying at 120-130 DEG C on the product to obtain the electrolytic manganese dioxide with the purity of more than or equal to 93%. The process provided by the invention is suitable for resource utilization of low-grade pyrolusite, and the obtained product is mainly used in the fields of lithium-manganese battery positive electrode materials, magnetic materials and catalyst carriers.

Water is added into manganese dioxide powder to prepare manganese slurry, ammonia water or ammonium bicarbonate is used for adjusting the pH value, sulfur-containing flue gas enters a desulfurizing tower to react with the manganese dioxide mineral powder and the manganese slurry to remove sulfur dioxide, manganese sulfate slurry is generated and can be used for obtaining high-purity manganese sulfate, and ammonium sulfate generated through the reaction can be recycled. The process is mild in production condition, SO2 in the flue gas is converted into available manganese sulfate, resource recycling of sulfur dioxide in the flue gas can be achieved, economic benefits are generated, meanwhile, environmental pollution is reduced, and a technical route is provided for sulfur-containing flue gas treatment and resource utilization. The produced manganese sulfate can be used for preparing high-quality battery-grade manganese sulfate, a raw material is provided for the new energy battery industry, and the market competitiveness of enterprises is improved. The process method provided by the invention accords with the concept of combining ecological environment protection and economic development, and has a relatively high application value.

A method of preparing a cathode active material composition involves combining a first cathode active material including recycled lithium 40 with a second cathode active material 41; wherein the ratio

The invention relates to the technical field of positive electrode precursors, in particular to a method for preparing a sulfate solution for a precursor by using a cobalt nickel hydroxide intermediate product and application of the sulfate solution. Performing acid leaching on the intermediate product, and then adding a flocculating agent to obtain a cobalt-nickel-manganese mixed solution and manganese slag; extracting the cobalt-nickel-manganese mixed solution and P507-C272, and reversely extracting a loaded organic phase to obtain a crude manganese sulfate solution; performing P204 impurity removal on the raffinate, recovering cobalt by using P507 to obtain a cobalt sulfate solution, and performing C272 nickel-magnesium separation to obtain a nickel sulfate solution; manganese slag is subjected to reduction leaching to obtain reduction leaching liquid, and then the reduction leaching liquid is mixed with a sodium carbonate solution to remove iron to obtain iron-removed liquid; mixing the iron-removed solution with the crude manganese sulfate solution, and removing calcium and magnesium to obtain a calcium-magnesium-removed solution; mixing the calcium and magnesium removed solution with an aluminum source to remove fluorine to obtain a fluorine removed solution; and mixing the fluorine-removed solution with sulfide to remove copper and zinc, adding alkali liquor to obtain a heavy-removed solution, and treating the heavy-removed solution with modified resin to obtain a refined manganese sulfate solution. The method is high in manganese recovery rate and low in treatment cost.

To provide a method for producing an industrially applicable manganese sulfate solution by selectively removing potassium from a sulfuric acid acidic manganese solution without generating jarosite and / or a method for producing a manganese oxide using the manganese sulfate solution.　The present invention is a method for producing a manganese sulfate solution, the method including a step for bringing a manganese sulfate solution containing potassium ions into contact with a zeolite having a molar ratio of silica to alumina of 6 or more and containing an oxygen 8-membered ring in the skeleton structure to adsorb the potassium ions to the zeolite, and a method for producing manganese oxide using the manganese sulfate solution obtained by the production method.

The invention discloses a method for preparing manganese sulfate by treating alkylated waste sulfuric acid through an oxidative degradation-adsorption method, and belongs to the technical field of industrial waste recycling. The method comprises the following steps: by taking pyrolusite as an oxidizing agent, efficiently oxidizing and degrading organic matters in the waste sulfuric acid in an acidic medium of alkylated waste sulfuric acid, and synchronously reducing and leaching manganese; according to the method, pyrite reduction leaching and H2O2 oxidative degradation (assisted by iron ion catalysis) are combined with activated carbon adsorption to deeply treat organic matters in a solution, and finally, high-purity manganese sulfate is prepared through impurity removal and crystallization. According to the method, harmlessness and recycling of the alkylated waste sulfuric acid are achieved, the process cost is low, secondary pollution is avoided, the purity of the manganese sulfate product reaches the industrial grade, and the method can be widely applied to the fields of batteries, fertilizers and the like and has remarkable environmental and economic benefits.

The utility model discloses a manganese sulfate MVR (Mechanical Vapor Recompression) crystallization solid-liquid continuous separation device which comprises a base, the supporting leg frame is arranged at the top of the base; the evaporator is arranged at the top of the supporting leg frame; the feeding hole is formed in the top of the evaporator; the stirring assembly is arranged in the evaporator; the stirring assembly comprises a driving motor, a rotating rod and a stirring frame; the top of the evaporator is fixedly connected with a driving motor; an output shaft of the driving motor is fixedly connected with a rotating rod through a coupling; and the outer wall of the rotating rod is fixedly connected with a stirring frame. According to the manganese sulfate MVR crystallization solid-liquid continuous separation device, through the arranged valve, materials in the evaporator can flow into the fluidization crystal device through the connecting pipe, crystals can be discharged from the outflow pipe through the arranged fluidization crystal device, and a solution can be pumped through the liquid pump, so that the crystallization effect is improved; and the solution is conveyed into the evaporator through the return pipe to be treated again, so that the solution can be continuously separated.

The invention discloses a device for preparing battery-grade high-purity manganese sulfate by absorbing sulfur dioxide through manganese carbonate ore, and belongs to the technical field of manganese sulfate preparation. Flue gas containing sulfur dioxide is introduced into an air cavity in a desulfurization tower through a gas inlet pipeline, so that manganese carbonate slurry can be in contact with the flue gas containing sulfur dioxide and absorb sulfur dioxide; a mixing paddle in the driving assembly rotates and stirs manganese carbonate slurry, the fluidity of the manganese carbonate slurry in the material supporting assembly is improved by matching with the guiding and conveying effect of a spiral blade on the manganese carbonate slurry, gas can overflow from a flow dividing hole in a material supporting frame after rising, a pump body works to enable a feeding pipe to extract the manganese carbonate slurry from the material supporting frame, and therefore the manganese carbonate slurry is pumped out of the material supporting frame. The manganese carbonate slurry falls on the material supporting frame through the discharging pipe and can be in contact with the rising gas again, so that the adsorption effect of the manganese carbonate slurry is improved in a multi-stage absorption mode, the adsorption capacity of manganese carbonate is fully exerted, and subsequent efficient preparation work of high-purity manganese sulfate is facilitated.

The invention relates to the field of resource utilization of industrial solid wastes, in particular to a method for preparing battery-grade manganese sulfate by purifying industrial solid wastes, which comprises the following steps: by taking silicomanganese metallurgical fly ash as a raw material, grinding, alkaline leaching, heating reaction and centrifugal separation to obtain manganese-containing filter residues; and the battery-grade manganese sulfate is prepared through the steps of sulfuric acid neutralization, filter pressing, oxalic acid-manganese monoxide refining, evaporative crystallization and the like. According to the method, all-component high-value utilization of elements such as manganese, silicon and potassium in the fly ash is achieved, the raw material recovery rate reaches 99.7% or above, the purity of the prepared manganese sulfate is larger than or equal to 99.5%, meanwhile, by-products such as potassium sulfate, sodium chloride, aluminum hydroxide and sludge containing 80% of silicon dioxide are produced, and remarkable economic benefits and ecological benefits are achieved.

A treatment process for crystallizing a metal sulfate involving pre-treating a feedstock comprising calcium, magnesium, and / or lithium impurities, the pre-treating involving pre-leaching the feedstock in the presence of a lixiviant, selectively extracting a first portion of any of the impurities from the feedstock, and forming a leached solution comprising an uncrystallized metal sulfate and any remaining impurities; and / or refining the leached solution and removing a second portion of any of the remaining impurities; and crystallizing the uncrystallized metal sulfate from the leached solution to form a crystallized metal sulfate. So processed, the crystallized metal sulfate may be battery-grade or electroplating-grade.

The invention discloses a method for dissolving and purifying a manganese dioxide-containing mineral. The method comprises the following steps: crushing and grading the manganese dioxide mineral for later use; washing the graded material with dilute sulphuric acid, and then centrifugally filtering to obtain filter residues and filtrate; preparing filter residues into a solid solution with water, adding concentrated sulfuric acid and methyl sulfate for primary dissolution, and filtering to obtain lead-containing minerals and filtrate; and after excessive manganese ore is added into the filtrate, MnCO3 and H2O2 are added, manganese ore which is not completely reacted and obtained through filtering is dissolved again, ammonia water is added into the filtrate for impurity removal, and a MnSO4 solution is obtained. According to the method, manganese dioxide-containing minerals are crushed to obtain particles, the particles are prepared into a solid material solution for secondary reduction acid leaching, the contact area of the mineral particles and reducing agents such as methyl sulfate, methanol and hydrogen peroxide is greatly increased, and methyl sulfate is used as the reducing agent, so that the method has the advantages of high reaction rate, high efficiency, safer storage and transportation and the like; the extraction rate of manganese ions is improved, and the extraction time is shortened.