44 results about "Pyrolusite" patented technology

The utility model discloses a system for preparing manganese monoxide from pyrolusite. The system comprises a crushing and grinding device, a pyrolysis device, a hydrothermal reaction device, an oxidation reaction device and a reduction reaction device. The crushing and ore grinding device, the pyrolysis device, the hydrothermal reaction device, the oxidation reaction device and the reduction reaction device are sequentially arranged in series. The pyrolusite is subjected to pretreatment such as pyrolysis, hydrothermal reaction and oxidation reaction, manganous-manganic oxide and manganic oxide contained in the pyrolusite are efficiently converted into manganese dioxide at low cost, the quality of a manganese monoxide product subjected to follow-up fluidization reduction is improved, and a foundation is laid for follow-up efficient leaching of manganese. And carbon dioxide released in the pyrolusite fluidization reduction process is recycled to prepare CO capable of being recycled for reduction, carbon resources are utilized to the maximum extent, and carbon emission is greatly reduced. The device has the characteristics of simple structure, convenience in operation, small equipment investment, small occupied field and the like.

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 discloses a low-cost advanced oxidation process catalyst for treating industrial organic wastewater as well as a preparation method and application thereof, and belongs to the field of preparation of environmental remediation materials and water pollution control. The preparation method of the catalyst is based on biochar and natural iron and manganese minerals, and comprises the following steps: firstly, crushing and sieving natural magnetite and pyrolusite, fully mixing according to a certain proportion, carrying out ball milling treatment, and obtaining miscellaneous element doped biochar by utilizing a pyrolysis method; and fully mixing the mixed element doped biochar and the iron manganese mineral composite catalyst, and then carrying out ball milling treatment under the protection of an inert atmosphere, so as to obtain the composite catalyst. The heteroelement-doped biochar contained in the catalyst promotes aggregation and electron transfer of pollutants, iron and manganese double metal elements can serve as active sites, the activation efficiency is remarkably improved through the synergistic effect of the iron and manganese double metal elements, and the degradation efficiency of the pollutants is improved.

The present invention discloses a septic tank sewage treatment device and its application, belonging to the field of environmental protection technology. The treatment device includes an inlet area, a sewage treatment unit and an outlet area. The sewage treatment unit includes a supporting layer, a mixed filler layer and a surface layer from bottom to top. Wetland plants are planted above the sewage treatment unit; the filler of the supporting layer is rock, the filler of the mixed filler layer is pyrolusite and pyrite, and the filler of the surface layer is biochar. The present invention adopts a bottom-in and top-out water inlet method to maintain the anaerobic environment of the treatment device, which can achieve efficient removal of organic matter, ammonia nitrogen, phosphate and soluble methane in the effluent of the septic tank, further alleviate the blockage of the treatment device and prevent the generation of endogenous methane, while preventing the leakage of heavy metals to cause secondary pollution.

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.

The invention discloses feeding and discharging equipment for high-purity manganese sulfate production, and belongs to the technical field of manganese sulfate production. The equipment aims at solving the problems that in existing high-purity manganese sulfate production, pyrolusite conveying is not uniform, the granularity is not uniform, the sulfuric acid filling efficiency and the leachate output efficiency are low, and potential safety hazards exist. The equipment comprises a base, an electric heating mixing and stirring box body, a spiral conveying mechanism and a feeding and discharging mechanism, the spiral conveying mechanism achieves automatic conveying and crushing of pyrolusite, the feeding and discharging mechanism achieves automatic filling of sulfuric acid and automatic output of leachate, and the equipment avoids material stacking through a homogenizing ring, a dispersing and homogenizing frame and a conical homogenizing disc. And the ventilation pipe and the electromagnetic valve are used for avoiding air pressure interference, the cleaning box body facilitates impurity cleaning, the automation rate of manganese sulfate production can be effectively improved, the production efficiency of manganese sulfate can be further improved, and stable operation of equipment is guaranteed.

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.

A multi-metal associated pyrolusite fluidization hydrogen-based ore phase conversion treatment method belongs to the technical field of pyrolusite reduction roasting, and comprises the following steps: refining raw ore to a required particle size standard to obtain an ore grinding product, drying the ore grinding product, scattering the ore grinding product to a uniform and loose state, and discharging the ore grinding product; the scattered pyrolusite product enters an ore phase conversion roasting furnace of a fluidized reduction roasting system and is preheated in advance in the air atmosphere, adsorbed water is removed, then N2 gas is introduced to empty air in the furnace, mixed gas of N2 and H2 is introduced, fluidized hydrogen group reduction is conducted, and a reduced product is obtained; and cooling the reduced product to normal temperature in N2 atmosphere to obtain a cooled product. According to the fluidized roasting technology adopted by the method, the high-purity bipartite ore can be obtained through efficient reduction, the reduction rate is greatly increased, accurate regulation and control of the reduced phase can be achieved by introducing nitrogen in the cooling stage, and compared with a traditional technology, the method has the environment-friendly advantage and application value.

The invention belongs to the technical field of manganese extraction in the manganese smelting industry, and particularly discloses a method for preparing manganese carbonate by roasting and reducing pyrolusite on the basis of copper tailings after flotation. According to the method, the copper tailings obtained after flotation serve as the reducing agent and are roasted with pyrolusite at the high temperature to obtain MnO, stable alpha-Fe2O3 and SiO2, then dilute acid with the extremely low concentration is adopted for leaching to obtain a manganese sulfate solution, the manganese leaching efficiency reaches up to 94% or above, iron is selectively separated, and industrial grade manganese carbonate is further prepared from the recycled manganese solution through a CO2 method. According to the method, resource utilization of the copper tailings after flotation is achieved, waste is turned into wealth, the cost of manganese recovery in the manganese smelting industry is reduced, and meanwhile good economic and environmental benefits are achieved.

The invention discloses a method for recovering manganese from pyrolusite waste residues. The method is characterized by comprising the following steps: crushing the pyrolusite waste residues, uniformly mixing and grinding, and drying; the method comprises the following steps: uniformly mixing dried pyrolusite waste residues with the ternary flux according to the claim 1, heating to 110 DEG C in a tubular furnace, roasting for 55-65 minutes at a constant temperature, continuously heating to 280 DEG C, continuously roasting for 25-35 minutes, then heating to 500 DEG C, continuously roasting for 55-65 minutes, cooling to room temperature after the reaction is completed, taking out a roasted residue sample, adding deionized water, leaching manganese sulfate at room temperature, filtering and separating, and drying to obtain the pyrolusite waste residues. Manganese sulfate crude liquid and leaching residues are obtained; metal oxides in the pyrolusite waste residues are reduced by the flux and then sulfated, so that the process of extracting manganese from the pyrolusite waste residues to produce high-purity manganous-manganic oxide is accelerated, and meanwhile, the problems of resource waste and environmental pollution caused by the pyrolusite waste residues are solved.

The invention discloses a control system for continuous leaching of pyrolusite or crude manganese dioxide, and relates to the technical field of hydrometallurgical equipment, in particular to a control system for wet continuous leaching of manganese sulfate from pyrolusite or crude manganese dioxide. Comprising a leaching device, a sulfur burning power generation device, a connecting pipeline, a pulping barrel feeding proportion control mechanism, a first-stage and second-stage absorption tower feeding control mechanism, a first-stage absorption tower discharging control mechanism and an automatic device for realizing continuous steady-state leaching of pyrolusite or crude manganese dioxide.

The invention provides a method for preparing manganese sulfate from low-grade pyrolusite based on sulfite circulation, a manganese-based material is prepared through the difference of the solubility of sulfite by utilizing the characteristic that the solubility of manganese sulfite is far smaller than that of calcium sulfite and magnesium sulfite, and manganese sulfate widely applied to the battery positive electrode industry is obtained. The by-product sulfur dioxide is used as a reducing agent to leach pyrolusite, the leaching cost is reduced, compared with a pyrite leaching method, the slag yield is reduced, recyclable ammonium sulfite is used as an intermediate manganese precipitation impurity removal agent, compared with an existing high-purity manganese sulfate preparation technology, the method is more efficient, the reagent cost is reduced, the quality of the prepared manganese sulfate is kept at the high-purity level, and the method is suitable for industrial production. The calcium and magnesium impurity removal effect is good, materials are simple, cost is low, recycling of main substances can be achieved, and environment friendliness is achieved.

The present invention relates to the technical field of manganese tetraoxide preparation, and specifically discloses a method for preparing battery-grade manganese trioxide, comprising the following steps: 1) crushing pyrolusite and mixing it with water to form a pulp, and absorbing sulfur dioxide gas by means of multi-stage spraying of the pulp to obtain a manganese sulfate reduction solution; 2) mixing the manganese sulfate reduction solution with a buffer to obtain a manganese sulfate pre-solution, and continuously mixing the manganese sulfate pre-solution with an alkali solution, a pH regulator, and an oxidant to carry out a reaction, and introducing air during the reaction to carry out an oxidation reaction; 3) aging the slurry after the reaction in step 2) is completed, filtering the aged slurry to obtain a filter residue, and drying and demagnetizing the filter residue to obtain battery-grade manganese trioxide. The present invention can effectively reduce energy consumption, simplify the production process, and can obtain battery-grade manganese trioxide with high purification, uniform particle size, stable quality, and low cost.

The application discloses a kind of high oxidation process catalysts for low-cost treatment of industrial organic wastewater and its preparation method and application, belong to environmental remediation material preparation and water pollution control field.The preparation of the catalyst is based on biochar, natural iron manganese mineral, first, after screening, natural magnetite and soft manganese ore are fully mixed in a certain proportion and are subjected to ball milling treatment, and the biochar doped with impurity elements is obtained by pyrolysis method, the impurity element doped biochar, iron manganese mineral composite catalyst is fully mixed, and then ball milling treatment is carried out under the protection of inert atmosphere, and the catalyst is obtained.The impurity element doped biochar contained in the catalyst promotes the aggregation of pollutants and electron transfer, and the iron manganese bimetallic elements can be used as active sites, and the synergistic effect between them significantly increases the activation efficiency and improves the degradation efficiency of pollutants.

The invention discloses a method for treating copper smelting refining slag by using pyrolusite, which comprises the following steps: step 1, respectively crushing and grinding the pyrolusite and the copper smelting refining slag, and mixing Cu2O in the copper smelting refining slag and MnO2 in the pyrolusite according to a molar ratio of 1: 1; 2, a sulfuric acid solution is added into the mixture of the pyrolusite and the copper smelting refining slag for leaching, and the liquid-solid ratio is 4: 1-11: 1 ml / g; and 3, Mn, Fe, As, Zn and the like in the leachate in the step 2 are removed through an extraction agent Lix984 extraction separation technology, and a pure mixed solution of the copper sulfate solution and the manganese sulfate solution is obtained after extraction and purification. According to the method, the pyrolusite is used as the oxidizing agent to treat the copper smelting refining slag, so that the aim of extracting valuable metals in the copper smelting refining slag while treating the pyrolusite can be achieved. The pyrolusite is adopted to directly leach the copper smelting refining slag to recover valuable metals such as copper and manganese in the copper smelting refining slag, so that on one hand, resource recycling is realized, and on the other hand, the purpose of reducing the cost is also achieved.

The invention discloses a method for preparing high-quality manganese monoxide by taking medium-low-grade pyrolusite as a raw material, and relates to the technical field of preparation of high-quality manganese monoxide products. The method comprises the following steps: crushing to prepare powder, blending coal, uniformly mixing, carrying out high-temperature reduction roasting through a reduction kiln to obtain manganese monoxide powder, cooling through a slag cooler, and carrying out magnetic separation in a magnetic separator to obtain concentrate which is a high-quality manganese monoxide product. By means of the magnetic separation process, the concentrate recovery rate reaches 50% or above, the resource utilization rate is remarkably increased, meanwhile, the battery-grade manganese sulfate product is prepared from the tailings through the leaching process, recycling of the tailings is achieved, and economic benefits are further increased; by optimizing the technological process, waste generation is reduced, the influence on the environment is reduced, the manganese content of the obtained manganese monoxide product reaches 60% or above, the quality requirement of high-quality manganese monoxide is met, and the manganese monoxide can be used for battery materials and can replace feed-grade manganese sulfate to be applied to multiple fields of animals and plants, catalysts, electronic materials and the like.

This invention belongs to the field of manganese tetroxide preparation technology, and discloses a method for preparing manganese tetroxide for drilling mud. In this invention, pyrolusite powder is subjected to a reducing leaching reaction using SO2 gas to obtain manganese sulfate leachate; then, it is mixed with a composite alkaline control solution composed of ammonia, anhydrous ethanol, and a surfactant to carry out a precipitation reaction, obtaining a spherical precursor; a catalyst and activator are then added to carry out an oxidation reaction to obtain a crude product, which is finally shaped in situ. This invention uses commercially available surfactants and, combined with specific process conditions, effectively controls the morphology of the precursor, achieving spherical particle growth and preliminary particle size control.

This invention provides a method for treating xanthate-based mineral processing wastewater using natural minerals, belonging to the field of water treatment technology. The method includes: adding pyrite powder to the xanthate-based mineral processing wastewater for activation treatment, converting xanthate groups into dixanthate groups, resulting in activated mineral processing wastewater; passing the activated wastewater through a galvanic cell filter layer while aeration is introduced, obtaining a first solution; and passing the first solution sequentially through a metal purification filter layer and a control filter layer to obtain mineral processing return water. The galvanic cell filter layer comprises pyrite, pyrolusite, and graphite. Through the coupling effect of pyrite and pyrolusite, oxygen in the air is activated into reactive oxygen free radicals and / or ozone, which oxidize and degrade the xanthate-based organic matter in the mineral processing wastewater.

A multi-metal associated pyrolusite hydrogen-based ore phase conversion system belongs to the technical field of pyrolusite reduction roasting, and specifically comprises a preheating oxidation subsystem, a hydrogen-based ore phase conversion subsystem, a cooling subsystem, a hot air circulation subsystem and a product collection pool, a gas material outlet of the preheating oxidation subsystem is communicated with a gas material inlet of the hydrogen-based mineral phase conversion subsystem, a discharge port of the hydrogen-based mineral phase conversion subsystem is communicated with a feed port of the cooling subsystem, and a discharge port of the cooling subsystem is communicated with the product collection pool; a gas inlet of the preheating oxidation subsystem is divided into two paths of input, the first path is communicated with a gas outlet of the hydrogen-based mineral phase conversion subsystem, and the second path is communicated with a gas outlet of the cooling subsystem; an air outlet of the preheating oxidation subsystem is communicated with an air inlet of the hot air circulation subsystem, and the hot air circulation subsystem is provided with an emptying port. By means of hydrogen group reduction, the ore phase structure is precisely regulated and controlled, precise ore phase conversion is achieved, and a new path is opened up for green development of complex manganese ore resources.

The invention relates to the technical field of petroleum proppant molding. The invention discloses a petroleum proppant particle molding control method and system based on machine learning, comprising first obtaining a base material weight and a base material purpose, determining an initial additive type according to the base material purpose and a first preset rule, obtaining an additive weight according to the base material weight and the initial additive type, determining a waste material type according to the initial additive type and a second preset rule, and then obtaining a waste weight through the additive weight and the waste type; if the initial additive type is chromite or pyrolusite, determining the chromite or pyrolusite as a target additive type; if the initial additive type is dolomite, determining the target additive type based on a first processing cost and a second processing cost; selecting additives according to demand or purpose, thereby improving the processing quality of the proppant.

The invention provides a low-energy-consumption preparation method of electrolytic manganese metal. The low-energy-consumption preparation method comprises the following steps that S1, pyrolusite and pyrite are mixed and then ground into mixed powder; s2, the mixed powder is placed in a multi-layer rotary roasting kiln to be roasted; s3, the mixed powder is sequentially subjected to first-stage countercurrent leaching, second-stage countercurrent leaching and third-stage countercurrent leaching, and leachate is obtained; s4, performing microfiltration on the leachate through a ceramic membrane to remove large-particle impurities, and then separating divalent manganese ions by adopting a roll type nanofiltration membrane, so that the concentration of the manganese ions in the solution is increased to 45g / L; and S5, the solution is added into an electrolytic tank for constant-temperature electrolysis, electrolytic manganese metal is obtained, a jacketed PP electrolytic tank is adopted as the electrolytic tank, a double-layer hollow structure of the electrolytic tank is filled with a polyurethane heat preservation layer, a 316L stainless steel negative plate is adopted, and a Pb-Ca-Sn alloy grid is adopted as a positive plate.

The application discloses a method and system for preparing manganese monoxide by adopting pyrolusite, through pretreatment of pyrolusite such as pyrolysis, hydrothermal reaction and oxidation reaction, low-cost and high-efficiency conversion of manganese tetroxide and manganese sesquioxide contained in the pyrolusite into manganese dioxide is realized, the product quality of the manganese monoxide prepared through subsequent fluidization reduction is improved, and a foundation is laid for subsequent high-efficiency leaching of manganese. The released carbon dioxide in the fluidization reduction process of the pyrolusite is recycled to prepare the recyclable CO for reduction, the carbon resources are maximally utilized, and the carbon emission is greatly reduced. The method has the characteristics of simple process flow, excellent operation condition, low fossil energy consumption, small environmental pollution, good economic benefit and environmental benefit and the like, and is expected to open up a more stable and efficient way for development and utilization of the pyrolusite.

The application discloses a pyrolusite gaseous arsenic adsorption material and a preparation method and application thereof, and belongs to the technical field of industrial flue gas pollution prevention and control. The adsorption material is prepared by pretreating pyrolusite and then ball-milling and activating the pyrolusite. The pyrolusite is mechanically activated and applied to the adsorption of gaseous arsenic in high-temperature industrial flue gas as an adsorbent. The application widens a new way for comprehensive utilization of pyrolusite resources and expands the raw material source of high-value-added adsorbents. The prepared pyrolusite gaseous arsenic adsorption material has more significant adsorption effect on gaseous arsenic than common pyrolusite, and the adsorption capacity of the prepared adsorption material on gaseous arsenic is 13.9 mg / g at 300 DEG C under the optimal condition, which is 1.62 times that of unactivated pyrolusite.

This invention belongs to the field of mineral processing technology and provides a method for the reduction preparation of manganese tetroxide. The method involves mixing pyrolusite and ascorbic acid solution, followed by secondary mixing with polyvinyl alcohol solution to obtain a mixed slurry. The mixed slurry is then spray-dried to obtain a precursor. The precursor is then calcined to obtain manganese tetroxide. This invention utilizes the reducing effect of ascorbic acid to convert inert tetravalent manganese in pyrolusite into active divalent manganese ions, which then enter the liquid phase. This allows for efficient separation of manganese from associated insoluble gangue impurities such as silicon and aluminum at the molecular level. Polyvinyl alcohol is introduced as a key structure-directing agent and framework support; the hydroxyl groups on the PVA molecular chain uniformly "anchor" manganese ions to the grid nodes. Through a low-temperature calcination process, a rich mesoporous structure is created in situ, inducing in-situ rearrangement and crystallization of manganese ions at the nanoscale, inhibiting excessive grain growth and preventing the formation of impurity phases at high temperatures.

This invention relates to a method for preparing high-purity manganese sulfate for lithium manganese iron phosphate precursors, belonging to the field of battery materials technology. This method aims to solve the problems of low ore reactivity leading to poor leaching efficiency and high energy consumption, difficulty in deep removal of calcium and magnesium impurities and significant environmental risks, and high energy consumption and poor product quality in the concentration and crystallization process of traditional pyrolusite manganese sulfate production. Key technical points include: using oxalic acid as a reducing agent for wet mechanical activation reduction leaching of pyrolusite; using a composite extraction system composed of P507 and TOA to deeply remove impurities from the leached slurry; returning a portion of the solid residue as a recycled grinding aid to the leaching step; and integrating thermally coupled back-extraction and evaporation crystallization operations in the same MVR system to achieve synergistic energy saving in impurity separation and product crystallization. This method is mainly used to prepare high-purity manganese sulfate with low impurity content, which can be used as a key precursor raw material for high-performance lithium manganese iron phosphate cathode materials.

The invention relates to a method for driving pyrolusite reduction and carbon-manganese co-production through rapid coal pyrolysis, which is characterized in that rapid coal pyrolysis is realized based on an infrared radiation heating technology, and high-activity reductive volatile components in the early stage of pyrolysis are synchronously utilized to carry out reduction reaction with pyrolusite, so that the synergistic preparation of a carbon-based product and a manganese resource is realized. The method comprises the following steps: performing pyrolysis on coal in an infrared pyrolysis reactor under the action of a high-intensity radiation heat source at 500-800 DEG C within milliseconds to second-level time to generate high-reducibility volatile components rich in H2, CO, CH4 and short-chain hydrocarbons and semicoke; the volatile component is directly introduced into a pyrolusite reduction reaction zone and is subjected to a gas-solid reduction reaction with MnO2 in pyrolusite at 600-900 DEG C, high-valence manganese oxide is converted into MnO or manganese metal, and meanwhile semicoke is produced to serve as a high value-added carbon material. According to the method, the reduction potential energy of volatile components is reserved to the maximum extent, more than 90% of active components directionally act on pyrolusite reduction, and the problems of high energy consumption, low reduction efficiency and insufficient added value of products in a traditional process are solved.

The invention discloses a method for preparing high-purity manganese carbonate from low-grade pyrolusite, which is characterized by comprising the following steps of: drying, crushing and screening the low-grade pyrolusite, uniformly mixing the low-grade pyrolusite with a flux, heating to 190 DEG C at the speed of 5-10 DEG C / min in a rotary tube furnace under the protection of nitrogen, roasting for 10-15 minutes at a constant temperature, heating to 350 DEG C at the speed of 10-15 DEG C / min, roasting for 20-25 minutes at a constant temperature, cooling to the room temperature, and cooling to room temperature to obtain the high-purity manganese carbonate. And after roasting is completed, naturally cooling to room temperature, adding deionized water to leach manganese chloride from a roasted sample, filtering and separating, carrying out graded purification and impurity removal on leachate, adding ammonium bicarbonate to convert manganese chloride into manganese carbonate, carrying out vacuum suction filtration, pulping and washing, and drying to obtain the high-purity manganese carbonate. And selective and efficient extraction of manganese in low-grade pyrolusite is realized.

The invention relates to the technical field of pyrolusite beneficiation, in particular to a low-intensity magnetic separation-reverse flotation process for pyrolusite based on hydrogen-based ore phase transformation. In the prior art, the pyrolusite wet reduction process is high in acid consumption and difficult in waste liquid treatment, and minerals are easy to oxidize and low in magnetism in the roasting process of the dry reduction process. In order to solve the problems, the method comprises the following steps: firstly, carrying out ore grinding to enable the particle size of most mineral aggregates to be less than 38 microns, then carrying out hydrogen-based mineral phase conversion suspension roasting, controlling the use amount of roasting gas, converting pyrolusite into acid-soluble billimanite with weak magnetism, carrying out crystal lattice conversion on quartz, and converting alpha.SiO2 into beta.SiO2, and gangue minerals are separated out through magnetic separation, then flotation is conducted on magnetic concentrate, manganese concentrate is obtained, and the manganese concentrate is high in grade and can serve as a high-activity raw material for leaching electrolytic manganese.

The invention discloses a method for producing manganous-manganic oxide from pyrolusite waste residues. The method comprises the following steps: (1) crushing, sieving and drying the pyrolusite waste residues; (2) mixing the dried pyrolusite waste residues with the flux in the claim 1, performing gradient roasting in a tubular furnace, then naturally cooling the roasted residues to room temperature, taking out the roasted residues, adding deionized water, performing water leaching at room temperature, and performing filtering separation to obtain a leached crude manganese sulfate leaching solution; (3) various impurity removal reagents are added into the crude manganese sulfate leachate for purification, and (4) ammonium bicarbonate is added into the fourth-time manganese sulfate purification liquid to obtain manganese carbonate precipitates, the manganese carbonate precipitates are washed with deionized water and calcined to obtain manganous-manganic oxide, and the manganous-manganic oxide is smashed, sanded, washed and dried to obtain the high-purity manganous-manganic oxide. The recovery rate of manganese reaches 99.4% or above, the method can be used for preparing high-purity manganous-manganic oxide, the energy consumption and reagent cost are lower, and meanwhile the problems of resource waste and environmental pollution caused by pyrolusite waste are solved.