475 results about "Pyrolusite" patented technology

The invention discloses a method for separating manganese and silver of manganese-silver ore and purifying manganese dipped solution thereof. The method comprises the following steps of: 1) pre-degrading and saccharifying plant byproducts comprising straws, hulls and slag; 2) reacting the product obtained in the step 1) with crude manganese-silver ore or enriched mixed concentrate dipped manganese; 3) separating, neutralizing and adsorbing the manganese dipped solution in the step 2) to obtain solution for preparing manganese sulfate and the like by further purification and crystallization; and 4) obtaining manganese dipped slag in the step 3), wherein the manganese dipped slag has high reaction activity, and the leaching time is short and the energy consumption is low during silver leaching treatment. The purifying method is also suitable for purifying the manganese dipped solution by adopting a reducing agent similar to rice bran and the like to treat pyrolusite or ferromanganese ore, and the treated manganese solution can be used for the production of manganese sulfate, electrolytic manganese and the like. The method has the characteristics of wide separation raw material source, reasonable process route, low equipment investment, low treatment cost, stable product performance and the like; and the manganese sulfate prepared by the method can meet the standard requirements of the industries such as chemical engineering, feed, agriculture and the like.

The invention discloses a new method for producing efficient active carbon by using biomass wastes (walnut shells, rape stems, wheat straws, Chinese medicinal dregs and the like) as raw materials, using pyrolusite as a hole forming agent and using zinc chloride as an active agent. The method comprises the following processes of: (1) drying the biomass waste raw materials till the water content is less than 15 percent, mechanically crushing the raw materials, and sieving the crushed raw materials with a sieve of 100 meshes; (2) adding 5 to 10 percent of pyrolusite into the raw materials, and mixing the pyrolusite and the raw materials uniformly; (3) soaking the pre-treated raw materials into 3 to 7mol/L zinc chloride solution for 24 hours, wherein the soaking ratio (the mass of the raw materials to the mass of the zinc chloride solution) is 1:1-1:2; (4) putting the soaked raw materials into a tubular furnace, introducing inert gas (such as nitrogen or carbon dioxide gas), heating to the temperature of between 400 and 600 DEG C, and performing one-step carbonization (synchronous carbonization and activation) for 0.5 to 1.5 hours; and (5) cooling, washing and drying the activated carbide to obtain the active carbon. The method improves the performance of the active carbon, reduces the preparation cost of the active carbon, and realizes recycling utilization.

The invention discloses a method for preparing electrolytic manganese metal with low-grade pyrolusite wet leaching, which comprises the following steps of: after low-grade pyrolusite is crushed and screened, mixing slurry with electrolytic manganese anolyte, adding sulfuric acid to control acidity, and reducing high-valent manganese insoluble in water into low-valent manganese readily soluble in water through a redox reaction by using reduced iron powder or waste iron scraps as a reducing agent; controlling certain acidity, reaction temperature and time, stirring and leaching, and then precipitating and filtering; purifying, decontaminating and separating a filter liquor to obtain a pure manganese sulfate solution; and electrolyzing the manganese sulfate solution to obtain an electrolytic manganese product, wherein the leaching rate of manganese is higher than 98%, the recovery rate of manganese is higher than 90%, and the purity of electrolytic manganese metal is higher than 99.8%. The method has the advantages that the raw materials of the reducing agent have wide sources and low price, the reaction time is short, the conditions of the leaching process are mild, the leaching rate of manganese is high, the purification process is simple, and the process route of the present carbonic acid manganese ore for preparing electrolytic manganese metal is not changed.

The invention discloses a pressurizing and reductive leaching method of pyrolusite powder. The method comprises the following steps of: a) mixing pyrolusite powder and iron sulfide powder to obtain mixed powder; b) adding a sulphuric acid solution in the mixed powder to pulp and obtain mixed slurry; c) adding the mixed slurry in an autoclave; d) injecting a gas in the autoclave to ensure that the inner pressure of the autoclave reaches a preset pressure value continuously and perform acid leaching under a pressure, then discharging to obtain an acid leaching mixture; and e) performing solid-liquid separation to the acid leaching mixture to obtain a manganese sulfate solution, wherein the pyrolusite powder contains 13-35wt% of manganese. According to the pressurizing and reductive leaching method of pyrolusite powder in the embodiment of the invention, by adopting the pressurizing and leaching method, the manganese in low-grade pyrolusite powder can be leached fast and effectively.

The invention discloses a synchronous desulphrization and denitration method of flue gas pyrolusite pulp for reclamation. The method mainly comprises the following steps: pyrolusite, water and metal-chelator are prepared into pulp which is taken as an absorbing agent; sulfur dioxide and nitrogen oxides in the flue gas are synchronously absorbed and removed by the absorbing agent; the flue gas is discharged when the purification reaches a standard; the primary product of the mixed mother solution of manganese sulfate and manganese nitrate is obtained after absorbing tail solution is purified; and by utilizing the different solubility of manganese sulfate and manganese nitrate at same temperature, the mixed mother solution is heated firstly to cause the manganese sulfate therein to be crystallized and separated, next, the left mother solution is cooled to cause the manganese nitrate therein to be crystallized and separated, and the left solution is returned to preparation pulp for recycling. No waster water is discharged in the whole process, thereby achieving the purposes of controlling waste by waste, recycling sulfur resources and improving the comprehensive utilization value of pyrolusite. The method is characterized by high desulphrization and denitration efficiency and manganese utilization rate, little secondary pollution, obvious economic benefit and the like.

A gray manganese ore leaching-out process is carried out by crushing, blending with water to obtain ore pulp, adding into sulfuric acid and sugar honey alcohol effluent, agitating at 50-98degree and reacting for 0.5-4hrs to obtain the final product. The leaching-out rate of manganese is >93%. It's simple, has gentle reactive condition and no environmental pollution.

The invention relates to a production method for high purity manganese sulfate. The production method is characterized in that pyrolusite is used as a raw material and is reduced by using a carbon fire method, then an acid is added for leaching, a vulcanizing agent is used to remove heavy metals consisting of cobalt and nickel, a fluoride is employed to remove calcium and magnesium, then filtering is carried out, ammonium bicarbonate or ammonium carbonate is added into a filtrate for deposition of manganese to realize separation of potassium and sodium, an obtained filtrate is used for recovery of the by-product ammonia sulfate for usage as an additive for metal manganese, the filter residue manganese carbonate is washed and then subjected to acid dissolution so as to obtain a manganese sulfate solution, and then crystallization is carried out to obtain a high purity manganese sulfate product, wherein mother liquor can be returned to a high purity system for reutilization. With the method provided by the invention, the high purity manganese sulfate product in which MnSO4 content is more than 99.8% and respective content of impurities consisting of Ca, Mg, K and Na is lower than 10 ppm is produced.

The invention discloses a method for restraining the generation of manganous dithionate in the process of leaching sulfur dioxide gas out of pyrolusite, which comprises the following main technical measures: (1) pyrolusite pulp is prepared by stirring and mixing in the proportion that 100-500g of pyrolusite and 0.2-100g of granular active carbon are added into 1L of water; (2) in a synchronous reaction process of absorbing the sulfur dioxide gas by the pyrolusite pulp, desulphurizing and leaching manganese, the pH value of the pyrolusite pulp is controlled to be lower than 3.5 by blowing oxygen or air into the pyrolusite pulp. The method restraining the generation of the manganous dithionate does not need to extra consume sulphuric acid and guarantee an oxido-reduction potential by extra adjusting the concentration of Fe<3+>/Fe<2+>, is easy to meet the requirement of industrial process production and can guarantee the concentration of a manganese sulfate mother liquor.

The invention relates to a method for extracting manganese from manganese-enriched slag. In the method, the manganese-enriched slag is subjected to alkali leaching on the basis of taking sulfuric acid as a leaching agent. The method comprises the following steps of: putting the manganese-enriched slag into a stirring tank, and adding sodium hydroxide solution to perform the alkali leaching; 2, standing, precipitating, preparing into a filter cake, and washing by water to obtain desiliconized and desulfurized manganese-enriched slag; 3, putting the desiliconized and desulfurized manganese-enriched slag into a leaching tank to perform acid leaching; and 4, separating by suction filtration to prepare acid leaching solution containing manganese sulfate, wherein before the acid leaching is performed, the water and pyrolusite also can be added to oxidize sulfur in the manganese-enriched slag further. In the method, gel silicic acid can be prevented during desilicication, so the actual extracting rate of the manganese; and hydrogen sulfide gas can be prevented from generating and escaping during desulfurization to prevent the adverse effect on operators. The method also has the advantages that the operation is simple and convenient, various reaction conditions are easy to control, and the loss of manganese-enriched ores in the integral process is small.

The invention relates to a method for circularly producing mangano-manganic oxide by manganous sulfate, which fulfills the aim of circularly producing the mangano-manganic oxide by the manganous sulfate by absorbing a mixed gas of sulfur dioxide and sulfur trioxide generated by calcining the manganous sulfate at a high temperature by mixed slurry which is formed by pyrolusite (or manganese dioxide), manganese carbonate and water. The method for producing the mangano-manganic oxide has the advantages of low cost, high product purity, no pollution and the like.

The invention provides a method for removing fluorine ion from manganese sulfate solution for producing electrolytic manganese metal, which comprises the following step of: when the manganese sulfate solution for producing the electrolytic manganese metal is prepared from rhodochrosite, pyrolusite, pyrite and vitriol, adding fluorine removing agent calcium carbonate and kieselguhr to remove the fluorine ion from the solution, so that the fluorine ion content in the manganese sulfate solution is less than or equal to 60mug/g. The method is simple to operate, the loss of the manganese in the solution can be avoided when the fluorine ion is removed, a cathode can not be corroded when a metal sheet is produced by the fluorine ion-free manganese sulfate solution in an electrolysis way, and the single plate is high in yield.

The invention discloses a method for quickly leaching gold and silver by using a mixed leaching agent, which comprises the following steps of: crushing gold-containing pyrite smelting slag, a sulfide-containing visible gold ore or/and a gold-containing oxidized ore serving as raw materials, conditioning the raw materials with water to form slurry, adding ammonium thiocyanate, thiocarbamide, urea and an oxidant, namely manganese dioxide or ferric chloride, into the ore slurry and stirring and leaching the mixed slurry to leach the gold and silver out. The method has the advantage that: the mixed leaching agent formed by adding the urea into the ammonium thiocyanate can quickly leach the gold and the silver out of the sulphur and arsen-containing gold ore by adding the urea with a low cost, particularly the gold and the silver which are contained in pyrolusite can be leached out with a lower cost. At the same time, beneficial elements in the ores can be comprehensively used.

The invention provides a method for treating ammonia nitrogen wastewater, which relates to a method for treating the ammonia nitrogen wastewater by using an adsorption method. The method is characterized in that in the treating process, a natural manganese mineral is used as an adsorbent to perform adsorption reaction with the ammonia nitrogen wastewater so as to remove the ammonia nitrogen in thewastewater. The natural manganese mineral is crushed into a manganese mineral adsorbent of 0-2 millimeters, the pH value of the wastewater containing the ammonia nitrogen is adjusted to be between 2and 12 by using acid or alkali, then the manganese mineral adsorbent contacts and is mixed with the ammonia nitrogen wastewater to perform adsorption, and the adsorption can be performed by adopting afixed bed adsorption column or in a stirring and mixing mode. When the fixed bed adsorption column is adopted for adsorption, the manganese mineral after being crushed is classified to remove fine particles for the best so as to improve the permeability of the adsorption column; and in the same way, when the stirring and mixing mode is adopted, the manganese mineral after being crushed is classified to remove coarse particles for the best so as to reduce the abrasion to equipment. The natural manganese mineral applicable to the method comprises a terrestrial manganese oxide mineral, an oceanpolymetallic nodule, an ocean cobalt-rich incrustation and a terrestrial manganese nodule, the natural manganese minerals usually contain manganese minerals of cryptomelane, todorokite, birnessite, vernadite, rancieite, pyrolusite and the like, have good pore structure and large specific surface area so as to have good adsorption property, and can be used as the adsorbent for treating the ammonianitrogen wastewater after being crushed into certain particle size, and the manganese minerals have the advantages of simple process, easy reproduction and stable performance.

The invention discloses a method for dry desulfurization and demercuration of sintering flue gas containing mercury by means of low-grade pyrolusite. The method comprises the steps that 1, the low-grade pyrolusite is obtained and placed in a reactor; 2, dedusting is conducted on the sintering flue gas to remove dust containing sulfur and mercury in the sintering flue gas, then the dedusted sintering flue gas with the temperature of 100-200 DEG C is introduced into the reactor at the flow rate of 1-8 L/min to enable the sintering flue gas to make contact with the low-grade pyrolusite, SO2 in the sintering flue gas reacts with the low-grade pyrolusite to achieve desulfurization, and residual mercury in the sintering flue gas is adsorbed by pyrolusite to achieve demercuration; 3, the sintering flue gas subjected to desulfurization and demercuration is directly discharged through an exhaust port of the reactor. The method has the advantages that desulfurization and demercuration cost is low, desulfurization and demercuration efficiency is high, the process is simple, and the recovery rate of byproducts is high.

The invention provides a method for leaching manganese sulfate from low grade pyrolusite. The method comprises the steps of crushing low grade pyrolusite and pyrite, placing crushed pyrolusite and pyrite in a leaching tank and mixing crushed pyrolusite and pyrite with sulfuric acid to prepare ore slurry. According to the invention, the mass percentage of manganese in pyrolusite is 9% to 21%, the mass ratio of pyrolusite to pyrite is 5-3:1, the molar concentration of sulfuric acid is 1 to 1.2 mol/L, and the mass ratio of sulfuric acid to pyrolusite and pyrite is 6-8:1; electrocatalytic reinforcement is carried out on the ore slurry so as to accelerate a reduction reaction. The method for leaching manganese sulfate from poor pyrolusite provided in the invention has the advantages of low cost, easy operation, short time, a high leaching rate of manganese, etc.

The present invention is improved process of extracting manganese form dialozite, and belongs to the field of wet metallurgy of dialozite. The materials include dialozite and sulfuric acid in the weight ratio of 1 to 0.3-0.8, as well as reductant in 1-18 wt% of dialozite and including sulfite, thiosulfate, SO2, iron pyrite, ascorbic acid and hydroxylamine. The process includes the following steps: filtering the acid leachate of dialozite, adding pyrolusite with MgO2 content of 15-90 wt%; ferrous compound eliminating reaction at 40-80 deg.c for over 20 min; and adding alkali, ammonia, lime, sodium carbonate, sodium bicarbonate and sodium hydroxide into the acid leachate of dialozite to regulate pH value to 5.0-8.0. The present invention has the advantages of less pyrolusite consumption,high Mg leaching rate and low Mg content in slag.

The invention relates to a production process for high purity manganese sulfate. The process is characterized in that pyrolusite powder is used as a raw material and is added into concentrated sulfuric acid for pretreatment, filtration is carried out after most impurities like calcium, magnesium, potassium and sodium are leached, an obtained filtrate is delivered to a common manganese sulfate production line for recovery and utilization, hydrogen peroxide used as a reducing agent is added into filter residue having undergone washing so as to reduce and leach pyrolusite powder, and a leachate undergoes condensation crystallization and primary recrystallization to obtain a high purity manganese sulfate product.

The invention discloses a new technology for preparing manganese sulfate solution which is used for electrolyzing manganese metal and recycling iron through the atmospheric pressure leaching of pyrolusite and iron scraps. The technology comprises the following steps: adding pyrolusite in a certain concentration of sulphuric acid solution, mixing evenly; adding iron scraps used as the reductant in a reaction tank, performing mechanical agitation for 1h-3h under different reaction temperatures to obtain reaction leachate; according to the changes of the reaction time and the pH value, adding heavy calcium carbonate and ammonia water in turn to adjust the pH value of the solution to 6.3-6.7; then adding sodium N,N-dimethyl dithiocarbaminate (SDD) to remove impurities such as heavy metal ions and purify; filtering, adding additive to obtain manganese sulfate solution used for electrolyzing manganese; and recycling iron from filter residue through alkali leaching and acid leaching to produce polyferric sulfate. The invention has the advantage that iron scraps are used as the reductant which have wide sources and rich raw materials and can be leached out under the atmospheric pressure; and iron scraps can be recycled to produce the water purification agent and have great economic benefit.

The invention relates to a remediation agent for leaching soil polluted by heavy metal chrome. The invention belongs to the technical field of heavy-metal-polluted soil remediation. The remediation agent comprises mixed components of, by weight: 95% to 99% of citric acid and 1% to 5% of pyrolusite. The leaching agent provided by the invention has advantages of low raw material cost, high remediation speed, good effect, and easy recycling of waste liquid.

The invention discloses a method for preparing manganese sulfate from waste water, waste sulphuric acid and a byproduct, namely iron vitriol obtained in the production of titanium white and low-grade pyrolusite or medium-grade pyrolusite with content of 10 to 20 percent, which has the advantages of low energy consumption, low cost and simple operation. The method comprises the following processes of grinding ore to prepare slurry, preparing reducing fluid, performing manganese leaching reaction, removing impurities, performing concentrative crystallization, performing centrifugal separation, drying, pulverizing and sieving and packaging, wherein the manganese leaching reaction is performed at the temperature of between 20 and 45 DEG C without vapor heating and pressurizing, so the method has the advantages of the comprehensively utilizing the iron vitriol, the waste water and the waste sulphuric acid during the production of the titanium white, turning waste into wealth, along with the leaching rate of manganese of more than 98 percent, the yield of the manganese of more than 85 percent, and good double benefits of environmental protection and circular economy development.

The invention relates to the technical field of catalyst preparation, in particular to an ozone catalyst which is low in cost and free of pollution and a preparation method of the ozone catalyst. A manganese sand filter material or pyrolusite ore serves as the raw material, adhesive, peptizer and a pore-expanding agent are added, and the ozone oxidation catalyst is finally formed through a series technologies of grinding, mixing, kneading, extrusion forming, drying and calcination and the like. According to the technical scheme, the catalyst is prepared by taking natural manganese sand or the pyrolusite ore as the raw material, the catalyst contains catalytic active components of manganese dioxide and iron, metallic elements do not need to be added, the production cost of the ozone catalyst is reduced, porous matter with the adsorptive action serves as the adhesive, the adsorption performance of the catalyst is effectively enhanced, the peptizer is added, the strength of the catalyst is enhanced, and certain pore expanding action is achieved. Due to the fact that the ozone catalyst is prepared through the method, nitrogen oxide pollution caused by calcination in the ordinary preparation process of an ozone catalytic oxidation catalyst is avoided, and the ozone catalyst and the preparation method thereof have the advantages of being low in cost, green and environmentally friendly.

The invention relates to a two ore combined process for treatment of laterite nickel ore and pyrolusite. The process includes the following steps: mixing laterite nickel ore with coal and roasting to obtain a ferrous oxide powder containing nickel and cobalt; leaching the ferrous oxide powder containing nickel and cobalt with concentrated sulfuric acid; after filtering, adding ammonium sulfate to the solution, controlling the concentration of H2SO4, adding pyrolusite to oxidize Fe<2+> into Fe<3+> and reduce Mn<4+> into Mn<2+>, and filtering to obtain a MnSO4-containing solution and an ammonium jarosite precipitate; adding a vulcanizing agent to the MnSO4-containing solution to produce sulfide nickel and cobalt sulfide precipitates, drying the precipitates to obtain a mixed powder of sulfide nickel and cobalt sulfide; and roasting the obtained ammonium jarosite precipitate, washing by water and drying to obtain crude iron red. The process can extract valuable metallic elements nickel, cobalt, iron and manganese from the two ores; and compared to respective treatment on the laterite nickel ore and manganese ore, the process saves production cost and improves production efficiency.

The invention provides a rare metal-based sludge activated carbon and application thereof in the removal of sulfur, ammonia and phosphorus. The rare metal-based sludge activated carbon includes sludge activated carbon and metal elements such as manganese, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium and the like, and is specifically prepared by a method comprising the following steps: mixing pyrolusite powder with activated sludge, adding a zinc chloride compounded activating agent into the mixture, activating the mixture at a high temperature, carbonizing the mixture to obtain pyrolusite compounded activated sludge, mixing the activated sludge with rare earth oxide powder and a chelating agent after the activated sludge is modified by potassium hydroxide solution, heating the mixture in a microwave oven, carbonizing the mixture to obtain rare earth compounded activated sludge, and mixing the compounded activated sludge to obtain a product. The rare metal-based sludge activated carbon prepared by the method has the advantages of high activity, high porosity, uniform pore size distribution, high adsorption capacity, capability of chelating a plurality of metals and microorganisms, high capacity of adsorbing sulfur, ammonia and phosphorus and high rate of removing the sulfur, the ammonia and the phosphorus in sewage and waste.