27 results about "Pyrolusite" patented technology

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.

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 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.

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.

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 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.

This application provides a method for the synergistic resource utilization of high-arsenic gold concentrate and low-grade silver-manganese ore, belonging to the field of hydrometallurgy. The method involves mixing high-arsenic gold concentrate and silver-manganese ore in a specific ratio, adding an oxidizing liquid to adjust the slurry concentration, and then mechanically intensifying the grinding process in an acid-resistant ball mill. During the grinding process, in the presence of the oxidizing liquid, pyrolusite in the silver-manganese ore and arsenopyrite in the high-arsenic gold concentrate undergo a redox reaction. Arsenic and iron enter the liquid phase in ionic form, while sulfur remains in the slag as elemental sulfur. After grinding, solid-liquid separation is performed to obtain arsenic-removed slag and arsenic-removed liquid. The arsenic-removed slag undergoes biological oxidation pretreatment, followed by solid-liquid separation to obtain oxidation slag and oxidation liquid. The oxidation slag is fed into a cyanidation system to recover gold and silver. The arsenic-removed liquid is treated to remove impurities, and manganese is recovered to obtain manganese salt products. The oxidation liquid and the tailings after manganese recovery are recycled. This application achieves the synergistic utilization of high-arsenic gold concentrate and low-grade pyrolusite ore through a mechanically intensified reaction.

The invention discloses a method for detecting manganese dithionate in a pyrolusite desulfurization solution, and belongs to the technical field of environmental hydrometallurgy. Drying potassium dichromate to constant weight, and preparing a potassium dichromate standard solution; filtering the desulfurized solution, transferring the filtrate into a COD (Chemical Oxygen Demand) digestion tube, adding a sulfuric acid solution and a potassium dichromate standard solution, and uniformly shaking to construct a reaction system; putting the digestion tube into a COD digestion instrument, setting temperature and time for digestion, transferring the solution into a conical flask, washing the digestion tube with water, and merging the washing solution into the conical flask to obtain a mixed solution; cooling the mixed solution to room temperature, titrating with an ammonium ferrous sulfate solution, dropwise adding an indicator, judging an end point according to color change, and recording solution consumption; calculating the content of residual potassium dichromate according to the concentration and consumption of the ammonium ferrous sulfate solution, and calculating the content of manganous dithionate in the desulfurization solution according to the difference between the initial amount and the residual amount of the potassium dichromate and the reaction stoichiometric ratio of the manganous dithionate to the potassium dichromate. The method is accurate and efficient in determination, simple and convenient to operate and low in reagent cost, and has remarkable industrial popularization value.

This invention discloses a blast furnace pulverized coal additive, which is composed of the following raw materials: 12-18 parts by weight of stearic acid-modified cerium oxide powder, 15-21 parts by weight of pyrolusite powder, 20-30 parts by weight of dolomite powder, 8-12 parts by weight of fluorite powder, and 5-8 parts by weight of calcium nitrate. The stearic acid-modified cerium oxide powder has a particle size between 400-600 mesh, while the particle size of the remaining raw material powders is between 100-200 mesh. This invention uses stearic acid to modify the surface of the cerium oxide powder, changing its surface from hydrophilic to hydrophobic. This results in stronger affinity with coal powder, which also has a hydrophobic surface, improving contact efficiency and thus increasing the utilization rate of the cerium oxide powder.

The present application relates to the technical field of pyrolusite beneficiation, and particularly relates to a weak magnetic separation-reverse flotation process based on hydrogen-based mineral phase conversion of pyrolusite. In the prior art, the wet reduction process of pyrolusite has the problems of high acid consumption and difficult waste liquid treatment, and the dry reduction process has the problems of easy oxidation of minerals and reduced magnetism in the roasting process. In view of the above problems, the present application first grinds the ore to make most of the ore particles smaller than 38 microns, and then performs hydrogen-based mineral phase conversion suspension roasting, controls the amount of roasting gas, converts the pyrolusite into weakly magnetic and easily acid-soluble rhodochrosite, and makes the quartz lattice transform from alpha SiO2 into beta SiO2. After the gangue minerals are separated by magnetic separation, the magnetic separation concentrate is subjected to flotation to obtain a manganese concentrate. The manganese concentrate has high grade and can be used as a raw material for high-activity leaching and electrolysis of manganese.

This invention discloses a method for efficiently leaching manganese from pyrolusite using acidophilic leaching microorganisms, relating to the fields of hydrometallurgy and biometallurgy. The method involves leaching pyrolusite using acidophilic leaching microorganisms, supplemented with pyrite as an auxiliary iron-sulfur source to enhance the leaching process. The initial pH of the leaching medium is 1.6, the pulp concentration is 120 g / L, and the inoculum concentration of the acidophilic leaching microorganisms is 10 × 10⁻⁶. 8 Under conditions of pyrolusite / pyrite mass ratio of 2:1 (cells / mL), the manganese leaching rate can reach 98.2% after 16 days of bioleaching. This invention significantly improves manganese leaching efficiency compared to a system without pyrite addition (3.2%). This invention helps solve the technical problems of high energy consumption and significant pollution in traditional pyrometallurgical and hydrometallurgical processes, and has advantages such as high leaching efficiency, environmental friendliness, low cost, and simple process. It is suitable for the green development and utilization of pyrolusite, especially low-grade pyrolusite resources.

According to the poly-generation system and method for enhancing pyrolusite reduction through co-pyrolysis of the low-rank coal and the biomass, through the two-section bed design of a pyrolysis reactor and a pyrolusite reduction reactor, reducing gases such as H2, CO and CH4 generated through co-pyrolysis of the low-rank coal and the biomass are directionally guided into the pyrolusite reduction reactor, and pyrolusite conversion is achieved. Pyrolysis gas, tar and semicoke products are synchronously produced at the temperature of 500-800 DEG C in the pyrolysis stage, and MnO2 is efficiently converted into MnO and Mn3O4 at the temperature of 400-600 DEG C in the reduction stage. The pyrolysis reactor and the reduction reactor are separately arranged, so that the pyrolysis temperature and the reduction temperature are independently regulated and controlled, the reduction gas yield is increased through biomass alkali metal catalysis, pyrolusite reduction activation energy is cooperatively reduced, the advantages of efficient resource conversion and low carbon emission are achieved, and the method is suitable for industrial production. And a new path is provided for collaborative utilization of low-rank coal, biomass and manganese ore resources.

The utility model discloses a low-loss manganese sulfate leaching system which comprises a first feeding device for feeding manganese monoxide, a second feeding device for feeding mother liquor, a third feeding device for feeding sulfuric acid, a reaction device, an adjusting device for feeding calcium carbonate and a cleaning device for supplying clear water, the first feeding device comprises a feeding hopper, a conveying belt and a slurrying pool, the feeding hopper is connected with the conveying belt, and the discharging end of the conveying belt is connected with the slurrying pool; the slurrying tank is also connected with the second feeding device; the slurrying tank, the third feeding device, the adjusting device and the cleaning device are all connected with the reaction device, and the reaction device is a closed reaction container. The device can realize fine processing production of continuous pyrolusite leaching, the process is controllable, the manganese content of slag is reduced, the manganese leaching rate is effectively improved, and the device has a good application prospect.

The application discloses a kind of normal temperature low acid fast extraction methods of manganese in pyrolusite, belong to mineral hydrometallurgy technical field.The method includes: pyrolusite is broken and ground to 80-200 mesh;Add sulfuric acid solution, control sulfuric acid concentration is 0.25-2.5mol / L, solid-liquid ratio is 1:5-1:10 g / mL;Add reducing agent, control reducing agent and manganese ore mass ratio is 0.13-0.43;In 20-30 ℃ normal temperature environment, stirring reaction is 5-10 minutes;Solid-liquid separation obtains manganese-containing leaching solution.In preferred scheme, reaction gas can be condensed and reused, or hydrogen peroxide is added after reaction to further improve the extraction rate of synergistic leaching.The application realizes normal temperature, low acid, fast extraction of manganese, reaction time is only 5-10 minutes, manganese extraction rate can reach 95% at most, energy consumption is reduced by more than 60%, acid consumption is greatly reduced, impurities are introduced little, solve the problem of traditional process high temperature, high acid, time-consuming, with significant energy saving and emission reduction and economic benefits.

The invention provides a method for extracting valuable metals from ores, and relates to the technical field of preparation of lithium ion battery positive electrode materials from mineral aggregates, and the method comprises the following steps: S1, taking pyrolusite, carrying out alkaline leaching, and then carrying out primary reduction to obtain reduced pyrolusite; and S2, pyrite and the reduced pyrolusite are taken to be mixed and ground, then acid leaching is carried out, after solid-liquid separation, a liquid phase is extracted, and a mixed solution containing iron and manganese is obtained. According to the method, the two low-value minerals including the pyrite and the pyrolusite are creatively mixed, valuable metal iron and manganese are efficiently extracted, the battery material can be prepared through subsequent short-distance treatment, and the additional value is high.

The application discloses a method for extracting manganese from soft manganese ore by ammonium sulfate composite molten salt reduction roasting, which comprises the following steps: drying and crushing the soft manganese ore, screening, mixing the screened soft manganese ore with flux, uniformly mixing, heating to 200 DEG C in a tube furnace under inert gas protection, constant temperature roasting, heating to 280 DEG C, constant temperature roasting, then heating to 605 DEG C, constant temperature roasting, naturally cooling to room temperature after roasting, taking out the roasting slag sample, adding deionized water to leach manganese sulfate at room temperature, filtering and separating, obtaining manganese sulfate crude liquid and leaching residue, grading and purifying the manganese sulfate crude liquid to remove impurities, converting the manganese sulfate into manganese carbonate by adopting a carbonate precipitation method, high-temperature calcination, and obtaining solid-state trimanganese tetraoxide. The method realizes efficient sulfation of MnO2 under inert gas protection by using a pyrogenic flux, forms soluble MnSO4, realizes water leaching of manganese from the roasting slag, and realizes a technical breakthrough in efficient extraction of manganese from the soft manganese ore.