Method of extracting manganese from manganese-bearing raw stock |
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IPC classes for russian patent Method of extracting manganese from manganese-bearing raw stock (RU 2484161):
 
 Method of processing manganese-containing material / 2448175
Method involves transfer of manganese and accompanying impurities into a solution through two-step treatment of the starting material with hydrochloric acid and absorption of chlorine with an alkaline solution. Further, impurities are separated to obtain a manganese salt solution which is then treated. The first step uses waste hydrochloric acid with concentration 1-10% with solid to liquid ratio equal to 1:(3-5). A manganese-containing residue is separated from the obtained pulp, where said residue is then treated at the second step with waste inhibited hydrochloric acid with concentration 20-24% and content of inhibitor of not less than 5 wt %, reaction with iron of which results in insoluble complex compounds, where said inhibitor is in form of quaternary ammonium salts, with molar ratio manganese:HCl=1.0:1.1. The insoluble residue of aluminosilicates is then separated and the manganese salt solution is then processed using existing methods.
Manganese dioxide obtaining method / 2444575
Manganese dioxide obtaining method involves dilution of manganese-containing raw material in nitric acid so that solution of manganese nitrates and nitrates of calcium, potassium, magnesium and sodium impurities contained in the ore is obtained. Then, thermal decomposition of nitrates in autoclave is performed. Thermal decomposition is performed at constant pressure drop in autoclave, starting from pressure of 0.6 MPa and reducing it to the end of the process to 0.15 MPa. At that, pulp is constantly mixed at thermal decomposition with the mixer rotating at speed of 1-15 rpm and with superimposition of vibration on it with frequency of 20-50 Hz. Method can be implemented at chemical plants provided with pressure autoclaves.
 Method of processing manganese ore / 2441086
Method involves grinding ore, mixing the ground ore with sodium bisulphate taken in stoichiometric amount required for binding manganese and impurities into sulphates. The mixture is calcined in three steps to obtain coal tar: at the first step at temperature 200-300°C for 1-2 hours, at the second step at temperature 400-500°C for 0.5-1.5 hours, at the third step at temperature 600-700°C for 2-4 hours. The coal tar is leached with water at temperature 40-80°C for 0.5-1 hour and weight ratio coal tar: water equal to 1:(3-4). After filtering the obtained pulp, sludge is separated and the filtrate is treated with sodium carbonate solution taken in stoichiometric amount required for binding and depositing manganese (II) and iron (II) compounds. After filtering the obtained suspension, the precipitate of manganese (II) and iron (II) carbonates is dried and washed to obtain a manganese concentrate. Calcination exhaust gases are absorbed with the filtrate from the manganese carbonate extraction step to obtain sodium bisulphate solution. Through evaporation of the obtained solution, crystallisation and drying, sodium bisulphate is obtained, which is taken for mixing with the ground ore to obtain the mixture.
 Method of processing manganese carbonate ore / 2441085
Method involves leaching alkali and alkali-earth metals with a solution of a chlorine-containing reagent and separating the insoluble residue containing manganese dioxide. The ore undergoes preliminary decarboxylation via thermal treatment at temperature 750-1000°C for 2-4 hours to obtain coal tar. The chlorine-containing reagent used when leaching the coal tar is 10-40% aqueous ammonium chloride solution, taken in weight ratio ore: ammonium chloride equal to 1:1-2. Leaching is carried out at temperature 20-100°C for 1-2 hours. After separating the insoluble residue, the filtrate is carbonised with exhaust gases from the ore decarboxylation step, followed by separation of the obtained calcium carbonate and return of the aqueous ammonium chloride solution to the coal tar leaching step.
 Procedure for processing waste chemical sources of current of manganese-zinc system for complex utilisation / 2431690
Procedure consists in separation of coal electrode and zinc cylinder, in flushing and dissolving in sulphuric acid. Also, flushing from ammonia chloride and zinc hydroxide is carried out with 0.2 M solution of sulphuric acid (H2SO4). Upon flushing residue of manganese oxide (IV) (MnO2), oxy-hydroxide of manganese (MnOOH) and coal mass (C) is crumbled in ball mills. Crumbled residue is dissolved in sulphuric solutions of concentration 0.05 mole/l containing 0.05-0.1 mole/l of oxalic acid at ratio of concentrations of ions of manganese and oxalic acid 1:5 at pH=1-2.2 and temperature of solution 80°C. Upon dissolving solution is filtered for removal of coal mass. Residues of zinc ions are removed from solution with isoamyl alcohol of 200 ml volume at presence of 2 M solution of ammonia thiocyanate and 0.5 M HCl, and there is performed neutralisation with 0.5 M solution of caustic soda (NaOH). Further, produced solution is evaporated at temperature 100°C to obtaining mass of crystalline compounds of composition sodium trioxalomanganate (IV) Na4[Mn(C2O4 2-)3] and salt of sodium oxalate (Na2C2O4). Produced mass is baked in atmosphere containing oxygen at temperature 400-500°C with production of MnO2 as a final product.
 Procedure for separation of cobalt from manganese / 2426806
Procedure consists in sorption of cobalt on complex forming ionite from manganese containing solution and of desorption of cobalt from ionite. Desorption of cobalt is performed with solution with pH value=4.5÷5.5 containing ions of copper and(or) nickel possessing higher affinity to functional groups of ionite, than cobalt.
Procedure for separation of scandium from manganese / 2416655
Procedure for separation of scandium from manganese consists in contacting solution containing scandium and manganese with extractant in interval of pH 2.9-3.3 during 30 minutes. Contacting is carried out with extraction of manganese. As extractant there is used 0.25 M solution of N-(hydroxi-5-nonobensyl-β-hydroxi-ethyl-methyl-amine (NBEA-2) in thinner.
Procedure for purification of manganese concentrates from phosphorus / 2395601
Invention refers to metallurgy, particularly to procedure for purification of manganese concentrates from phosphorus. The procedure consists in agglomeration of concentrate with sodium salts at 950-1000°C and weight ratio 1:0.4, and in successive water leaching with transfer of phosphorus into solution. Further concentrate is filtered and dried. Also leaching is carried out under effect of ultrasonic oscillations of 18·103-22·103 Hz per second frequency during 15-30 minutes. Finished concentrate is filtered and dried in ultrasonic fields of 18·103-22·103 Hz per second frequency.
Procedure for production of manganese (versions) / 2393254
Thermal reduction by heating charge containing reducer and manganese compound is performed at temperature 700-750°C in inert atmosphere. As manganese compound there is used manganese oxide (III) or manganese oxide (IV), or manganese chloride, while as reducer there is used hydride of lithium taken in excess at amount of 25-50 wt %. Also lithium chloride is additionally introduced into charge at ratio of lithium to lithium hydride taken in excess in moles equal to 2:1. Heated charge is conditioned during 30-90 min. Further manganese is extracted out of reaction mixture by means of cooling, flushing with water and filtering.
 Method of electrolytic production of manganese from ferrous alloys production wastes / 2389533
Invention relates can be used in metallurgy, electronics and in production of pigments and welding electrodes. Wastes of production of ferrous alloys containing, mainly, manganese represent slimes of fume gases washing from furnaces producing ferromanganese and silicon manganese. Said wastes are directed for thermal sulphating 1 that comprises furnace processing of material fed from mixer wherein said wastes have been subjected to treatment by acid with flow rate approximating to stoichiometric. Teflon chutes are used inside the furnace to produce SO2. Then hydrometallurgical phase is performed consisting of vatting stage 2, primary 3 and secondary 4 washing stages and that of conditioning. Vatting is carried out at intensive mixing in reactor with coating that regulates acidity using anolyte of electolyser or synthetic anolyte. Primary washing stage 3 is carried out in the same reactor till pH increases to values approximating to neutral one by removing, mainly, iron and aluminium. Produced fine pulp is filtered in pressure filter, flushed by water, preferably, in the same pressure filter, to produce inert wastes. Fine pulp flushing water is added into the mixer or used again to concentrate manganese therein. At secondary flushing stage 4, zinc impurity is removed by settling ZnS. Solution obtained after conditioning 5, is directed to electrolysis 6 to produce electrolytic manganese.
 Method to process sludge of neutralisation of acid mine waters / 2482198
Invention relates to the field of hydrometallurgy of heavy non-ferrous metals. The method for processing of sludges of neutralisation of acid mine waters includes its preliminary grinding, afterwards sulfuric leaching is carried out during mixing by means of treatment of the sludge with acid mine waters and sulfuric acid and addition of iminodiacetatic ampholyte for simultaneous sorption of copper and zinc. Ampholyte is separated from the produced pulp, and its desorption is carried out with sulfuric acid with formation of desorbed iminodiacetic ampholyte and sulfate solution. The desorbed ampholyte is returned to the stage of leaching and simultaneous sorption. From the sulfate solution by means of electrolysis copper is serially extracted, and then - zinc. The treated sulfate solution is returned to the stage of desorption. The produced pulp after separation of ampholyte from it is neutralised with lime, afterwards it is separated with solid residue and liquid part. The remaining solid residue is dried and ground with production of a gypsum-containing end product.
 Method of uranium ore processing / 2481411
Proposed process comprises crushing and grinding the ore, sulfuric acid leaching with addition of nitrogen acid as an oxidiser. Then, uranium is extracted and cleaned of impurities with the help of extractive agents mix to wash saturated extractive agent with the solution of sulfuric acid. After extraction, uranium is re-extracted to obtain uranium concentrate by means of 8-10%-solution of sodium carbonate. Uranium is deposited from re-extracted product by hydrogen peroxide with 50-100%-surplus from stoichiometry at equilibrium pH 3.6-4.2, mixing interval of 1- 1.5 h and sedimentation time of, at least, 1 h.
Method of metal extraction from silicate nickel ores / 2478127
Proposed method comprises ore pretreatment by crushing, classification and grading, biological degradation of ore silicate minerals by multiple ore interaction with silicate bacteria cultural medium without mixing with replacement of said cultural medium at pH, at least, 0.4. Then, metals are leached from biological degradation cakes by cultural solutions after extraction of silicon therefrom and additions of sulfuric acid to concentration of 50-450 g/l. After leaching, metals are extracted form cake leaching solution. Note here that cultural medium is replaced on reaching redox potential in solution of minus 250 mV. After biological degradation and before leaching, cakes are flushed with water.
 Complex processing method of carbon-silicic black-shale ores / 2477327
Invention refers to complex processing method of carbon-silicic black-shale ores, which contain vanadium, uranium, molybdenum and rare-earth elements. The above method involves ore crushing to the particle size of not more than 0.2 mm and two leaching stages. Oxidation sulphuric-acid leaching is performed at atmospheric pressure. Autoclave oxidation sulphuric-acid leaching is performed at the temperature of 130-150°C in presence of oxygen-containing gas and addition of a substance forming nitrogen oxide, as a catalyst of oxygen oxidation. Ion-exchange sorption of uranium, molybdenum, vanadium and rare-earth elements is performed from the obtained product solution.
Method of extracting rare-earth elements from phosphogypsum / 2473708
Invention relates to the technology of producing compounds of rare-earth elements during complex processing of apatites, particularly extraction of rare-earth elements from phosphogypsum. The method involves preparation of pulp from phosphogypsum and sorption of rare-earth elements on a sorbent. The pulp is prepared from ground phosphogypsum and sulphuric acid solution with pH=0.5-2.5 until achieving liquid:solid ratio of 4-7. Sorption is carried out directly from the phosphogypsum pulp on a sorbent with sulphuric acid functional groups for 5-7 hours with solid:sorbent ratio of 4-7.
 Method to extract metals from sulphide mineral raw materials / 2468098
Method includes leaching of ground raw materials in a solution of sulphuric acid with concentration of more than 2.0 g/l, containing ions of trivalent iron of more than 10-12 g/l, while mixing, at the temperature up to 100°C, solid phase content to 60%, at least in two serially connected reservoirs. The pulp discharged from the last reservoir is separated into solid and liquid phases. At the same time the solid phase is returned for leaching into the first reservoir. Iron oxidation in the liquid phase is carried out with iron-oxidising bacteria adsorbed on a neutral carrier at the pH 1.4-2.2 and 90°C with aeration by gas containing oxygen and carbonic acid. Then the liquid phase is returned after iron oxidation into leaching reservoirs, and metals are extracted from the produced phases. Besides, leaching is carried out with aeration by oxygen-containing gas. The pulp discharged from each reservoir is separated into solid and liquid phases. The solid phase is sent for leaching to the next reservoir, and the liquid phase is prepared prior to oxidation with bacteria. Duration of leaching is increased in each subsequent reservoir.
 Method to process metal-containing sulphide mineral raw materials with extraction of metals / 2468097
Invention relates to the method for extraction of metals from metal-containing sulphide mineral raw materials. The method includes leaching with mixing of a sulphuric acid solution in presence of trivalent iron ions in at least two serially connected tubs, separation of leaching products into liquid and solid phases, iron oxidation in a liquid phase, return of the liquid phase after iron oxidation into leaching reservoirs, intermediate extraction of metals from liquid phases. At the same time the initial raw materials prior to leaching are exposed to preliminary acid treatment at PH=0.8-1.4, S:L=1:1. Leaching is carried out in two stages at the temperature of 75-95°, PH=1.0-1.2 and S:L=1:(3-6), concentration of trivalent iron ions of 30-45 g/l at each stage with separation of leaching products after each stage into liquid and solid phases and iron oxidation in a liquid phase after each stage and with extraction of metals at each stage from liquid phases after iron oxidation. To the first stage raw materials exposed to preliminary acid treatment are sent, and to the second stage - a solid phase is sent, produced after separation of leaching products at the first stage. The liquid phase, which was produced after oxidation of iron at the second stage, is returned to the last leaching reservoir of the same stage.
Method of processing titanium-containing concentrate / 2467953
Invention can be used in chemical industry. The method of processing titanium-containing concentrate involves decomposition of the titanium-containing concentrate with sulphuric acid solution while heating with transfer of titanium into the sulphuric acid solution and separating the solid residue. Ammonium sulphate is added to the titanium-containing sulphuric acid solution in an amount which ensures concentration thereof in the solution of 300-450 g/l, with crystallisation of the ammonium-titanium-containing solid phase which is separated and dissolved in water to obtain sulphuric acid solution with pH=1-2. A silicon-sodium reagent is added to the obtained solution and sodium hydroxide is also added to ensure molar ratio TiO2:SiO2:Na2O=1:(0.75-5.5):(0.5-5) in the suspension. The silicon-sodium reagent used is crystalline sodium silicate or liquid sodium glass. The suspension is held in sealed conditions at temperature 150-250°C for 20-40 hours to form a titanium-silicon sodium-containing residue which is separated, washed with water and dried at 70-150°C to obtain the end product.
Method of phosphogypsum processing for manufacture of concentrate of rare-earth elements and gypsum / 2458999
Method of phosphogypsum processing involves leaching of phosphogypsum with sulphuric acid solution with change-over of phosphorus and rare-earth elements to the solution, and gypsum residues is obtained, rare-earth elements are extracted from the solution and the gypsum residue is neutralised with the main calcium compound. In addition, leaching is performed with sulphuric acid solution with concentration of 1-5 wt %. After that, rare-earth elements are extracted from the solution by sorption using sulfocationite in hydrogen or ammonia form with further desorption of rare-earth elements with ammonia sulphate solution. After desorption to the obtained strippant there added is ammonia or ammonium carbonate with deposition and separation of hydroxide or carbon-bearing concentrate of rare-earth elements. Extraction of rare-earth elements of medium and yttrium groups to concentrates is 41-67% and 28-51.4% respectively. Specific consumption of neutralising calcium compound per 1 kg of phosphogypsum has been reduced at least by 1.6 times.
 Method of producing vanadium oxide / 2454369
Invention relates to vanadium oxide extraction. The method of producing vanadium oxide involves preparation of starting vanadium-containing material for burning, burning with lime treatment, leaching with sulphuric acid, separating the solid substance and liquid, precipitation of ammonium polyvanadate with an ammonium salt and removing ammonia by calcination or reduction to obtain vanadium oxide. The solid starting material used at said steps has total amount of alkali metal of not more than 0.3 wt % and total amount of Cl- and NO3 - ions of not more than 0.1 wt %, and the liquid starting material has total amount of alkali metal of not more than 0.1 g/l and total amount of of Cl- and NO3 - ions of not more than 0.1 g/l.
 Method for reprocessing of metal sulfide-containing products / 2245380
Invention relates to reprocessing of metal sulfide-containing ores, products and waste of ore concentrating and metallurgy industry. Method includes leaching in sulfuric acid solution with concentration of 1.8-35 g/dm3 at 0-1500C in presence of iron(III) ions with concentration more than 1 g/dm3 and iron regeneration using element compounds having built-in voltage when transition from highest valence to lowest one higher the same of iron. Compounds are added into solution when increasing iron(II) ion concentration. Method is useful in leaching by bawl, percolation, heap, and underground processes, as well as in metal recovering into solution, development of rare and noble metals, impregnated in metal sulfides. Invention affords the ability to reduce power requirement, increase effectiveness of equipment utilization, and decrease reagent consumption.
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FIELD: metallurgy. SUBSTANCE: method of processing manganese oxide materials containing heterovalent manganese oxides comprises leaching crushed raw stock by sulfuric acid aqueous solution in the presence of bivalent iron sulphate, iron precipitation and manganese extraction from productional solution. Note here that said leaching is performed on adding reducing agent in the form of metal iron or iron sulphate (Fe2+) at 60-95°C for 60-300 min. Leaching is carried out at initial concentration of H2SO4 in leaching solution of up to 100 g/dm3 and final acidity in productional solution relative to hydrogen ion exponent pH<2. EFFECT: higher manganese yield. 1 tbl
Method for processing manganese oxide materials containing unequally valence manganese oxides, comprising, leaching the crushed material with an aqueous solution of sulfuric acid in the presence of sulfate, ferrous iron, filtration, precipitation of iron, followed by separation of manganese from the solution, wherein the process is carried out with the addition of the reducing agent in the form of iron metal or iron sulfate (Fe2+) at a temperature of 60-95°C, duration 60-300 min and an initial concentration of H2SO4in the leaching solution to 100 g/DM3and the final acid concentration in the final solution by hydrogen pH<2. The invention relates to the field of hydrometallurgy, in particular to methods for extracting manganese from the mn containing materials containing carbonates and oxides of manganese (Mn2+and Mn3+). A method of refining the mn containing raw materials and production of a solution of sulphate of manganese leaching of raw materials in solutions of sulphuric acid taken in the stoichiometric content in relation to the soluble components of the mn containing feedstock at a temperature of 75.5°C with supply in a solution of hot sulphurous gas produced from roasting iron pyrites sulfuric acid production. Cleaning solutions of impurities are Stripping in what suham from the pulp residue content of SO 2with the subsequent deposition of impurities molochnosokovoj components at pH 4.5-7.0 and a temperature of 40-70°C. the resulting mn containing solutions [1. Patent No. 2082797 (Russia). Published: 27.06.1997. Shchepkin A.A., Bubnov VK Barnov V.M. and others]. This method is implemented on a "virgin mining and chemical combine", Kazakhstan. A method of refining poor manganese ore, for example, marine iron-manganese nodules with a high content of phosphorus and silicon which includes thermochemical processing of raw materials ammonium chloride in the ratio of ammonium chloride to the manganese in the ore (2.0 to 2.5), at a temperature of 150-400°C To produce the chloride of manganese, which are subsequently leached out with water, and gases containing ammonia, directed to obtain ammonium chloride. The solutions obtained from water leaching, purified from iron, silicon and phosphorus, are sent to the electrolysis to extract manganese. The obtained manganese concentrate is used to obtain ferromanganese [2. Patent No. 2174156 (Russia). Published: 27.09.2001. Tails VP, Chistov LB, Malov H. and others]. There is a method of processing manganese ore, ferromanganese nodules and waste from various industries sulfate method, which consists in leaching of mn containing raw material in sulphuric acid solutions 77-98% stagione the practical ratio acid, required for the binding of manganese sulfate in the presence of the regenerative solution containing sulfite ion. The recovery solution is proposed to use bisulfite solution potassium concentration of 20-40%, with a pH of 5.2 to 6.0 [3. Patent No. 2223340 (Russia). Published: 10.02.2004. Nosenkov A.N., Trunev SV, Dmitrevsky B.A., Triosence N.N.]. The disadvantages of the above methods is their ecologicall (use of SO2, NH3), low economic efficiency (the use of expensive autoclave process at T=150-400°C and costly chemicals, including potassium bisulfite), final manganese concentrates suitable for use in ferrous metallurgy production of ferromanganese, which speaks to their lack of purity. The closest in technical essence is a way of extracting manganese from ores and products of their processing, comprising leaching the crushed material with a solution of sulfuric acid in the presence of sulfate, ferrous iron, filtration, precipitation of iron, followed by separation of manganese from solution [4. Chitrik and other "Getting low-phosphorus manganese concentrates. - Kyiv: Tekhnika. 1969, 164-166]. The disadvantage of this method, on a set of attributes which is the prototype of the proposed izopet the tion, is the lack of optimum leaching for maximum extraction of manganese in the solution of the oxide and carbonate raw materials. The technical result is to increase the extraction of manganese in the solution from recyclable raw materials through the development and improvement regimes hydrometallurgical processing. The technical result is achieved in that in the method for processing manganese raw material containing unequally valence carbonates of manganese, comprising leaching the crushed material with an aqueous solution of sulfuric acid in the presence of sulfate, ferrous iron, filtration, precipitation of iron, followed by separation of manganese from solution, the leaching process is carried out by adding a reducing agent in the form of iron metal or iron sulfate (Fe2+) at a temperature of 60-95°C, duration 60-300 min and an initial concentration of H2SO4in the leaching solution to 100 g/DM3and the final acid concentration in the final solution by hydrogen pH<2. Thanks to the optimization of solution temperature and time is achieved by increasing the activity of chemical transformations and completeness of chemical reactions with restorative additives. Supplements of iron metal or iron sulfate (Fe2+ ) encourage the rapid recovery of manganese in the form cyclotorsion(1, 2, 3).
In our experiments we used technogenic raw material, such as waste from the processing of complex ores. The raw materials were videlacele sulfuric acid solution with an initial concentration of 100 g/DM3at T/W=1/3 for 1-5 hours at a temperature of 25-95°C with the addition of iron metal and iron sulfate (Fe2+to restore Mn3+→Mn2+. The results of the 6 series of experiments presented in the table.
The results of the experiments can be judged that the extraction of manganese in solution increases with increasing temperature and increasing time of leaching. The maximum achieved extract was 86.7% was in the 5th series of experiments at a temperature of 95°C and time of leaching 5 hours with the addition of Femeth. Adding FeSO4the best leaching achieved in the 4th series of experiments at 60°C and time of leaching 1 hour and was 83,44%. When you exit temperature and time indicators of the process and in the absence of remedial additives slow extraction of manganese to the level of 50%. Thus, the proposed method provides high recovery of manganese, up to 86.7%. Method for processing manganese oxide materials containing unequally valence manganese oxides, comprising leaching the crushed material with an aqueous solution of sulfuric acid in the presence of sulfate, ferrous iron, filtration, precipitation of iron, followed by separation of manganese from production solution, characterized in that the leaching is performed with the addition of the reduction is vitela in the form of iron metal or iron sulfate (Fe 2+) at a temperature of 60-95°C, duration 60-300 min and an initial concentration of H2SO4in the leaching solution to 100 g/DM3and the final pH in the final solution by hydrogen pH<2.
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