Extraction method of metals from metal-containing mineral raw material

FIELD: metallurgy.

SUBSTANCE: method involves crushing of raw material, its heaping in the form of a pile, pre-treatment of raw material in the pile, treatment of the pile with a leaching solution, dilution of metals and obtaining of productive solution with removal of metals from it. At that, pre-treatment is performed by supplying separate solutions or mixture of solutions containing surface active substance and hypochlorite to the pile. Treatment with the leaching solution is performed by means of the solution obtained by mixing in the pile volume at supply to it of separate solutions or mixture of solutions containing hypochlorite, surface-active substance and/or mineral acid. In the leaching solution there used are mixtures of mineral acids or in-series introduced mineral acids. Supply points of the above solutions to the pile can be different.

EFFECT: increasing the efficiency of the process cycle at reduction of costs and emission of hazardous gases.

5 cl, 9 tbl, 6 ex

 

The invention relates to metallurgical and mining industry, mainly the heap leaching of metals from metal-containing mineral raw materials such as ore and/or ore concentrates, industrial metal-containing waste dumps, slimes, and others, and may find application in metallurgical and mining enterprises of nonferrous metallurgy. The invention can be used in the extraction of minerals underground and heap leaching of crushed metal-containing mineral raw materials, in particular of slag and clinker iron and steel industries. Distinctive features of this material is relatively low content of non-ferrous and noble metals with high concentrations of compounds of silicon, aluminum, iron and calcium in the form of persistent vitreous structures arising at high temperatures. This complicates the extraction of valuable and precious metals.

Numerous examples in the literature describe the use of nitrogen-containing heterocyclic aromatic compounds for the direct extraction of precious metals, particularly gold and platinum group metals (Patent US 4654145 31.03.1987, SW 3/34)using chloride solutions, and as an active extractants are used quinoline. Directly retrieve only the gold, and platinoid is then extracted from the organic phase. This method is not suitable for recycling from metallurgical wastes. The method for extracting gold and silver (Patent RU 2027785, 1991.08.01), allowing to increase the selectivity of the extraction of precious metals and simplify the process. Essence: the original gold product is pulverized, mixed with a solution of ferrocyanide sodium or potassium. The treatment is carried out in an autoclave at 100-180°C and the pressure of compressed air 5-20 ATM. This method of periodic action and is not applicable for complex processing of metallurgical waste. Also known hydrometallurgical method for extracting rare metals (patent US 4752412, SW 3/44, SW 3/00, 21.06.1988), namely, that pre-ground raw material is placed in an open container containing the mixed, heated to boiling (preferably up to 82°C) acid aqueous solution with a pH acidity equal to 3 and below, containing acid, taken from a series: nitric, hydrochloric, sulfuric, phosphoric, hydrofluoric, acetic acid. The process is conducted under continuous bubbling in the reaction mixture is introduced from the outside of the UV-ozone generator gaseous mixture of oxidants produced during irradiation of a mixture of molecular oxygen and water vapor mercury vapor high-pressure lamps. Further to highlight oxidized in acidic solution of rare metals from the matrix and formation of a productive solution containing complexes of rare metals, increase the pH acidity of the reaction mixture to 11 by the addition of lime and alkalis and is introduced into the reaction mixture of complexing agents for rare metals, taken from a series: cyanide, sodium hypochlorite, THIOCARBAMATE, thiourea or iron (II) hypochlorite, which form the oxidized rare metals, water-soluble chelates. After a certain time leaching of rare metals under these conditions, and the formation of the mother liquor saturated chelate complexes of rare metals, the supply of oxidants stop, the mother liquor is separated from the insoluble raw materials and extract useful components from the mother liquor using standard technology. The oxidant is injected into the reaction mixture in the gas phase. The effectiveness of this process in an open vessel is not high due to the low speed diffusive exchange and low-speed equilibrium on the boundary of the gas-liquid. The main components, for example, ozone and oxygen is poorly soluble in aqueous liquids. In addition, the implementation of the method have large deadweight losses of gaseous oxidant under conditions of ozonation gas through the liquid reaction mixture in an open vessel and due to the high temperature keeping process. This process also does not provide a sufficient concentration of oxidant in the reaction is ionic surface resistant particles of the matrix raw material, in aqueous solution, due to diffuse restrictions on the boundary surface of the solution matrix. Reduces the efficiency of the process increases the number of operations and time duration of the process proposed separate maintenance oxidation of the matrix and rare metals in acidic medium and subsequent, already in an alkaline environment, getting the mother liquor and dissolved in it complexes of rare metals. There is a risk of sedimentation of the formed calcium sulfate micropores and microcracks on the surface of the hard particles of the raw material, which reduces the extraction of valuable components. This method does not provide the dissection of the components that are resistant to peroxide oxidation. The method is cost-effective only for rare metals and their elevated concentrations, which is rare. There are also known methods of heap leaching of ores, including the preparation of the ore, the formation of its stack and its irrigation leaching solution penetrating into the array of stacks, the dissolution of metal and drainage productive solution. As pls apply a weak solution of sulphuric acid, a solution of iron sulfate and sulfuric acid, soda solution, sodium cyanide and other (see Kalabin A.I. Mining underground leaching): Atomizdat, 1969, P.95-319; Rysev VP, Sadykov, BC, Fazlullah M.I. Experience heap leach gold Mining magazine. - 1994. No. 12 - P.8-10). Modifying them is way ore heap leaching, which includes ore crushing, ore pelletizing (cement, lime, polymers, natural compounds like humic acids and other), dumping ore in the form of a trapezoidal stacks, application of stacks of ore leaching solution (for gold ore cyanide such as sodium cyanide concentration of 0.2...0.4 g/l with a density of irrigation 150...170 l/(m2·day)), infiltration of the solution into an array of stacks, the dissolution of metal and drainage enriched solvent with subsequent sorption on activated carbon or zinc shavings (see Dementiev V.E., Tatarinov, A.P., Gudkov S. Main aspects of heap leaching of gold-bearing raw materials. Mining magazine. - 2001. No. 5 - P.53-55). The disadvantages of these ways: reducing the rate of leaching and the completeness of extraction of metal due to clogging of the pore space at the bottom of the pile due to segregation pieces of ore and migration of fine particles (clay, silt) from the top to the bottom of the pile. At low outside temperatures the rate of leaching is also sharply decreases due to the increase in viscosity pls. The method for extracting metals from ores containing natural sorbents: charcoal, silica gel, alumina, zeolites and others (Patent RU 2118384, IPC6 SW 3/04, 27.08.1998), which includes the preparation of the ore for leaching supply of leach solution into the ore, collecting productive solution and the precipitation of the metal from the pregnant solution by ion exchangers. The key to this method is the use of surface-active substances (surfactants) for obstacles re-deposition of gold ions on the surface contained in the ore natural sorbents. For the extraction of metals by this method is passed a productive solutions through synthetic ion-exchange resins, ion exchangers, so in this way postulated limits for PAHs, namely: the length of the carbon chains of the surfactant is greater than the length of the carbon chains of natural sorbents contained in the ore, but less than the length of the carbon chains of the resins, which precipitated metal from the pregnant solution. Because of this, gold can move from a productive solution to the ion, which then get metal by known techniques. The disadvantages of this method: the need for joint selection of resins, surfactants, with its own interval, and other components of the leach solution, high consumption and high cost of a number of resins and surfactants that meet these requirements, the difficulties of using this method for large complex processing of raw materials containing different metals. In addition, molecules PA the long hydrocarbon chain is not only able to lower the surface tension, but it is also effective to gidrofobizirovan solid hydrophilic surface of clay particles and metal, providing the distribution of the hydrocarbon film on the metal surfaces and clay mineral species. As a result, the contact boundary between the mineral particle - metal" may be a layer of non-polar liquid having a low work cohesion, defined nonspecific dispersion interactions. This prevents the leaching of metals, especially already present in the rock in the form of micro inclusions ("microcanonical"), which is typical for precious metals. The efficiency of their extraction can dramatically decrease. In metallurgical industrial waste, for example, clinker steel production, industrial ashes in the form of such inclusions are often present and non-precious metals: iron and non-ferrous metals. This method is designed to extract gold ion exchangers and used for complex processing of large-capacity waste difficult. There is also known a method of extracting precious metals, including materials handling circulating washing solution mixture of hydrochloric and sulphuric acids with the addition of hydrogen peroxide as oxidant and subsequent processing of the productive solution ("Rh, PtandPdRecoveryfromNewandApentAutomativecatalysts" // WuKooYinget. al. PreciousMetals, 1993, N 17, p.343-34). In this way the addition of hydrogen peroxide in a solution of hydrochloric and sulfuric acids will lead to increased consumption of reagents, to the generation and release of gaseous chlorine in the amount of reducing environmental safety and cleanliness of the process. Modification of this method - a method of extracting precious metals from materials containing them, comprising leaching the material with a solution containing chloride ions, the introduction of a leaching solution of sulfuric acid and hydrogen peroxide, the subsequent processing of productive solution with the extraction of precious metals and the return of the recycled solution for leaching, characterized in that the sulfuric acid and hydrogen peroxide are injected into the leach solution in the form of a mixture, and mixing is carried out by introducing hydrogen peroxide in sulfuric acid at a molar ratio of H2SO4:H2O2>1 and when cooled (patent RU 2167211, IPC7SW 11/00, SW 3/06, 20.05.2001). This method requires significant amounts of hydrogen peroxide, which is inconvenient for large-scale production. Also known is a method of processing waste containing copper, zinc, silver and gold (patent RU 2109076, SW 7/00, SW 11/00, 20.04.1998), which deals with waste management, mainly metallurgical production with the extraction of copper and zinc, silver and gold in the form of visokoparan the x concentrates. The method is based on processing of source material water-salt solutions containing oxidant to enhance leaching of valuable components, primarily silver and gold, with subsequent sorption of gold and silver, selective extraction preconcentration of copper and zinc and their electrodeposition. The source material is subjected to oxidative leaching, feeding directly into the pulp chlorine gas. Technical result is achieved by simultaneous extraction of these metals in solution in the leaching step, for which the solvent metals use with complexing properties of alkaline ammonium salt solutions containing oxidizing agent. As oxidant use of active chlorine is dosed into the slurry leaching to maintain a given potential. Subsequent extraction preconcentration and separation of non-ferrous metals allows you to extract all the valuable components of the solution in the commodity form. The sequence of operations according to the method: produce simultaneous leaching of the metals specified by the solution of the resulting productive solution spend the sorption of gold and silver on activated carbon, and the concentration of gold and silver precedes subsequent sequential extraction to separate the extraction of copper and zinc from the pregnant solution by organic extractants, of which these metals are extracted by sulfuric acid solutions, exposed and then processed for final selection of metals. Obtained after extraction of copper raffinate, before extraction of zinc, optionally purified from copper, silver and gold cementation, and adsorbed on active coal gold and silver is extracted by cyanidation.

Disadvantages:

1. Difficulties for use in heap leaching due to uncontrolled emissions of gaseous chlorine, and also because of the inability to maintain uniform feed of chlorine through the material of the pile.

2. The complexity, the multi-stage circuit and the intricacy of its implementation for the industrial metal waste, mainly metallurgical origin. Iron contained in large quantities in metallurgical waste in this way is not retrieved.

3. Using cyanidation on a large scale, which is dangerous for the implementation of near industrial centers, where and are, as a rule, the piles of metallurgical plants.

There is also known a method of extracting precious metals from waste sulfuric acid production - pyrite Ogarkov, obtained by roasting iron pyrites - pyrite (Patent RU 2034062, IPC6SW 11/00, SW 11/08, 1995.04.30). The essence of the calcine is subjected to acid about is abode, then separate the liquid phase, extract the copper and zinc, solid phase gospelchor in the presence of lime, aeration is carried out at elevated temperatures and pressure, after which Tianyou in the presence of the sorbent. The thickened slurry cinder investquest, classified, Sands gospelcause to the content of the class 0.01 mm 95-98%, drain classifier, condensed to liquid to solid equal to 1.5 to 2.5, is oxidized in an autoclave at 80-150°C, 1-3 ATM; next Izvestkovaya pulp after cooling is either to conventional cyanidation with a temperature of 30-40°C, or cyanide at a temperature of 60-80°C and pressure. Then the sorption leaching with saturated output of gold and silver resin, which after regeneration back into the cycle of sorption and solutions are sent for refining. Condensed waste pulp goes to the destruction of cyanides or in an autoclave (100-160°C, 1-3 ATM), or other known methods. This method allows to increase by 20-30% removing precious metals, but is not applicable for complex processing of large-scale metallurgical wastes. For separation of gold from refractory ore and waste mining known method (U.S. Patent N 4552589, SW 11/08, 1985). In this way the source material is crushed, mixed with an additional agent and heated under pressure n is less than 0.7 ATM to a temperature of not lower than 150°C. The mixture is then treated with an acid solution, cooled and recovered gold cyanidation. The lack of significant losses associated gold due to its low extraction. Variant of the method of selection of gold (Patent RU 2094502, IPC6SW 11/00, 1997.10.27) by processing of ores, concentrates and wastes in the mining industry, containing a significant amount of bound gold and gold, preserved in various minerals ("hidden gold"). By the way the source material is crushed, mixed with alkalis in relation to the source material not less than 1:1 and heated to a temperature of at least 150°C, after which the mixture is leached with water, defend, sludge is filtered and the sediment filter is treated with hydrochloric acid, after which the gold is extracted using bromoform. Dignity - this method retrieves up to 90% gold. Cons: the selection is only subjected to gold, which is free and available for interaction with the leaching agent, in addition, to implement the method requires a lot of alkali (quantity of alkali is comparable to the raw material) and the entire weight of the mixture of raw materials with alkali it is necessary to heat to a temperature of at least 150°C. specific examples of the application - up to 200-250°C). This method is not applicable, is not advantageous for complex processing of metallurgical waste.

The known method of the treatment of precious metals from ores chloride-hypochlorite solution. The recommended composition of the solution contains 3% sodium chloride and 0.3% of sodium hypochlorite. Extraction of metals from solution is carried out by electrodeposition at the cathode or in other ways. The solution after adding the hypochlorite again used for leaching (Pat. US 5169503, SW 3/00, SW 11/00, 08.12.1992). Recovery of maintenance for pixelates lead either by electrolysis or by the addition of hypochlorite. To slow down the decomposition of pixelates can be added cyanuric acid. For processing carbonaceous ores known method for leaching gold and silver in alkaline medium at pH 8-13 concentrated solution of sodium chloride 5,0-20,0% salt hypochlorite 0,25-2,0%. After cementation of gold and silver, zinc, sodium hypochlorite is regenerated by electrolysis and the solution is returned to the leaching (US 4342592, SW 3/00, SW 3/10, 03.08.1982). These methods do not allow to effectively extract the precious metals in underground leaching of ores, because of the high viscosity of the concentrated solutions and brines is a decrease in the permeability of the ore body, and the use of alkaline solutions will lead to clogging of the pore space during the swelling of shale. There is also known a method of extracting gold from ores, including pre-acidification of ore with an acid solution and the leaching of gold chloride solutions (EN 2093672, MP is 6EV 43/28, 1997.10.20). Disadvantages: the method is intended only for the extraction of gold and the increasing concentration of sodium ions entering the solution with hypochlorite, more than 5-7 g/l, leads to ion-exchange clogging, reducing the permeability of the ore and the efficiency of extraction of gold. In addition, in the more concentrated acids to increase productivity and, consequently, the pH is less than 1, when the input of sodium hypochlorite, is rapid decomposition of intensive gas, which reduces the content of the oxidizing agent in solution, causes the emergence of the gas clogging and does not effectively lead to the leaching process. The known method of selective leaching of metals (EP 1281779, IPC7SW 011/00, 03.02.2003), in which mineral raw materials in contact in an aqueous solution with oxidizing agents sequentially in the following order: in the presence of oxygen, then oxygen and ozone and the oxygen, ozone, and the third reagent. After application of each step is the separation of the solid and liquid phases. The disadvantages of the method: processing of raw materials is carried out in aqueous solution, which requires large tanks, reactors, pipelines corrosion performance, powerful sources of oxygen and ozone, leaching technology complex includes three operations divisions, the lack of selective behaviour is ity extraction of metals. Known close to to this invention, a method for processing refractory mineral raw materials containing metals (RU 2265068, IPC7SW 3/06, 2005.11.27)includes leaching resistant mineral materials in aqueous acid solution with a concentration of 1.8 to 50 g/DM3active oxygen in the presence of ferric ions and the extraction of metals from the resulting leachate. After leaching resistant mineral raw materials, carry out the separation of the obtained product in liquid and solid phases and extraction of metals produced from liquid and/or solid phase. Leaching use containing or forming active oxygen oxidizers: ozone, or hydrogen peroxide or singlet oxygen, or atomic oxygen, or oxygen-containing radicals, or a mixture of at least two of the listed oxidants, and as oxygen-containing radical can be used superoxide, hydrophilicity, hydroxyl, and others. When leaching resistant mineral raw materials use a solution of an inorganic acid, preferably sulfuric or hydrochloric. This leaching resistant mineral raw materials with the use of an oxidant containing, or constituting an active form of oxygen, is carried out at atmospheric pressure or greater at 40-95°C. Removing vidaloca the different metals can be performed without separation of the products of the leaching phase, for example, sorption method, or from solid and liquid phases of the leachate after their separation. By this method the leaching resistant mineral raw materials is carried out in tanks with a solution, ultraviolet irradiation, with hydroacoustic impact on the solution, providing a cavitation mode, and in the hydrodynamic regime, when tightening the threads of the solution containing the gas and solid phase, with the possible excitation in solution vibrational mixing, resonant waves, or vibrations, or shock waves. Leaching of mineral raw materials perform with its ultrasonic treatment prior and/or during the process of leaching, for which it is proposed to use an inorganic acid, preferably sulfuric or hydrochloric. The disadvantages of this method: significant energy consumption for its implementation required anti-corrosion performance of expensive equipment: abrasion resistant piping, separators, reactors, high capacity, operating at elevated temperatures and pressures, are equipped with powerful generators, ultrasound, cavitation, shock waves, ultraviolet light, powerful sources of oxygen and ozone, which are difficult to create, which determines the complexity of the implementation of the invention. Such leaching solutions are highly corrosive and should be applied in Dor is hostease equipment which is inert with respect to these substances. In addition, ultrasonic and other treatments that cause additional wear on the equipment, which significantly reduces the economic effect of the implementation of this method. This method is difficult for complex processing of large-capacity waste metallurgical industry. The known method for the hydrometallurgical extraction of rare metals from technologically resistant materials (Patent RU 2114196, IPC6SW 3/04, 27.06.1998), which is resistant raw materials are crushed, placed in a sealed vessel containing complexing agents for rare metals, a solution of a halogen acid, nitrous acid. The vessel serves oxygen. The process is conducted at a certain pH value of the reaction mixture, the pressure and the half-wave potential for the recovery of oxidants sufficient time, which is chosen from the condition of opening of the matrix raw material for maximum oxidation and extraction of rare metals from the matrix and education of the mother liquor, containing dissolved complexes and oxides of rare metals. The extraction of rare metals from the mother liquor produced by known methods. This method is periodic, requires a special vessel pressure control many parameters of the process and is not suitable for processing depleted by heavy metals is Aria. The invention relates to the field oxide technologically resistant materials, in particular, to the processing of ash waste from coal burning to extract rare earth and radioactive metals. For such control requires complex and expensive equipment, which significantly reduces the economic effect of this method, especially for the processing of such poor rare metal raw materials, such as ash and slag wastes from the combustion of energy coal. System chloride-hypochlorite, as follows from the analysis of the analogies that can be used as an alternative to cyanide. But here there is a technical contradiction. In the methods, uses bestiality leach solution containing the oxidizing agent on the basis of hypochlorite and acid, the probability of decomposition leach solution due to the decomposition of hypochlorite with the release of chlorine at the stage of preparation of the leach solution. These methods, as shown above, is not suitable for heap leaching due to uncontrolled emissions of gaseous chlorine, and also because of the inability to maintain uniform feed of chlorine through the material of the pile, because the movement of gas through the fine material is mainly through the channels. In addition, the process is conducted in an acidic region, where the solubility of chlorine is low (<0.5%), and high is eucast, and that is why even for VAT leaching oxidation potential of chlorine and related oxidants is not fully used. This causes the need for additional control measures, process, solution, stabilization, requires constant monitoring of such solutions, limits the operating range of concentrations of the components and the application of such solutions. Known hydrometallurgical method for extracting metals from refractory sulfide ore (EN 2086682, IPC6SW 11/00, SW 11/08, 1997.08.10). The method comprises grinding the ore to a nominal size of at least 0,64 cm, acidification with mineral acid, the processing of acidified ore with nitric acid. The processed ore is placed on top of the impermeable collector in the form of a heap permeable layer through which is dispersed an aqueous solution of nitric acid, and then spend the aqueous leaching heap of ore. After washing its ore leached and extract precious metals from the leach solution. Generated during the pre-oxidation of the ore NOx gases fed into the generator of nitric acid for conversion to nitric acid, which recycle to process the ore.

Stage:

a) grinding the ore to a nominal amount not less than 0,64 cm;

b) treating the crushed ore with a mineral acid (preferably sulfuric acid) the pH encountered a mixture of about 2 or below (preferably to a pH of about 1);

c) processing acidified ore with nitric acid: 5 to 200% of the stoichiometric need to interact with the ore and extract the gas of NOx released from the ore;

d) optional addition of acid binders to ore, treated with nitric acid, to form agglomerates of ore, are able to maintain the porous layer of ore, while maintaining the binder and ore in contact with each other during the exposure time, sufficient to preserve the ore agglomerates of its specific forms, and retrieval of NOx emitted at this stage (d);

e) placing the thus treated ore in the form of a heap permeable ore layer on top of the impermeable collector;

f) heap processing permeable layer of ore is continuous or discontinuous dispersion of an aqueous solution of nitric acid through the layer;

(g) the office of the residual acid fluid from the heap permeable ore layer;

h) water rinsing the heap permeable ore layer to remove the nitric acid solution and separating the leaching of the ore layer;

i) the introduction of a NOx gas, extracted in stage (C) and (d), the generator of nitric acid to convert NOx to nitric acid and recycling mentioned nitric acid for use in the processing mentioned ore;

j) optional processing heap permeable ore layer dost the exact amount of calcium ions, sodium or magnesium in alkaline medium (preferably calcium carbonate, calcium hydroxide, sodium hydroxide or magnesium hydroxide to increase the pH of the liquid removed from the layer, up to 10 or above;

k) processing heap permeable ore layer is continuous or discontinuous dispersion leaching reagent for precious metals through the layer;

l) the Department leach solution containing dissolved precious metals from the heap permeable ore layer and removing the aforementioned noble metals from the leach solution.

This method is the closest analog to the proposed technical solution. This method is aimed at removing the harmful action of the fumes of nitrogen oxides emitted during the processing of ore with nitric acid cyanide solution under irrigation, but has its own disadvantages: requires initial acidification ore a large amount of mineral acid, and carbonate ores there is a risk of sedimentation of the formed gypsum, as described in the patent. Required only for the initial processing of a large quantity of concentrated sulfuric acid. Then the ore in a rotary mixers treated with nitric acid and poured a heap (pile). This requires a powerful corrosion-resistant hardware, with the possibility conveyors, etc., moreover, the time required implementation contact ore and nitric acid, as noted in the patent. You must catch the oxides of nitrogen (environmental and economic considerations), and ore aglomerados to save the porous layer with the introduction of the acid. The capture of nitrogen oxides is difficult, expensive and requires an extensive network of faucets, pipes, traps (all - in corrosion-resistant version). This method contains many operations preliminary acid treatment, including hazardous transport operations transportation of minerals, soaked in concentrated mineral acids. The method comprises flushing from acid neutralization pH (with translation in the alkaline region to pH=10)contained in the pores of the pieces of ore mineral acids for mandatory training to cyanide leaching of gold. A significant disadvantage of this method is low efficiency and duration of the process of extracting metals by passing solutions of reagents through a lot of rock (up to 61 m in description) under the action of gravitational forces. It depends on the filtration properties of the pile, the density of the irrigation system. In particular, in almost any organization technology supply solutions on the stack is the heterogeneity of the leaching layers you who OTE heap: in the upper layers of solid material can be fully contacted with the reagent solutions, and forth movement of the solutions occurs at the most affordable guides pore space with the formation of fissures, fistulas and wood thrown rocks, which drastically reduces the contact surface ore and reagent and accordingly the efficiency of the method is only applicable for processing by cyanidation gold-bearing sulfide ores that can recoup all costs.

The prototype is designed for the recovery of precious metals, so numerous operations on it are preliminary to effect the opening of the ore with the extraction of precious metals cyanidation, which is the washing of ore from acid, alkali neutralization ore processed.

In addition to crushing, the prototype includes operations:

- pre-treatment of feedstock mineral acid in a rotary apparatus;

- additional processing nitric acid (rotary phones) to ensure agglomeration of pieces of ore to eliminate clogging appeared ore fines;

- the dumping of processed ore in the form of stacks ("heap permeable layer");

- irrigation received stacks of nitric acid;

- trapping nitrogen oxides created during the processing of the ore with nitric acid, with their recycling for recycling of nitric acid for treatment of piles;

- the office of the residual nitrate what about the solution from the ore;

- water rinse of the pile to remove the acid from the ore;

Department of leaching from ore;

- additional processing stacks alkaline solution containing carbonates and/or hydroxides of alkali and/or alkaline earth metals, to change the pH of the liquid impregnating the stack, to pH=10 or more;

direct leaching of the ore by passing through the pile leaching reagent (cyanide leaching);

- separation from the pile productive solution containing dissolved precious metals, the extraction of these metals.

All multi-stage processing of the prototype is aimed at the preparation of the ore for leaching. Preferred mechanochemical processing of ore in several stages nitric acid. In this way a stack of ores can also be subjected to the stages of processing without movement or destruction of heap layers: first it is treated by heap oxidation by adding nitric acid and the final oxidation of the remaining sulfide compounds, then it is washed with water, successively treated with lime at the stage of neutralization and finally treated by heap leaching with cyanide sodium, all of these stages you can spend in any way without destroying the layer. But this variant of the method according to the prototype simplified and does not provide wetting azo is Noah acid on the surface of all pieces of ore, unlike shown in the prototype joint mechanochemical processing pieces of ore with nitric acid in a special rotary apparatus for the removal of heat due to the fumes of nitrogen oxides and their subsequent regeneration of nitric acid in special apparatuses and direction derived nitric acid to the processing of ore, as described in the prototype.

Thus, you need a way to increase the efficiency of metal extraction, preferably with heap leaching of metals from ores, heavy industrial metal-containing waste, for example, steel production, including those containing gold, which would increase the speed and completeness of processing without the use of toxic reagents, reducing the emission of harmful gases into the atmosphere and with the simplification of the process.

From the analysis of the available technical level it is evident the presence of a number of contradictions characteristic of the known methods of extracting metals from ores and industrial wastes. The extraction of precious, non-ferrous metals and iron in a single technological cycle is extremely difficult, and the return is provided only in the extraction of gold, which requires a high dispersion of the grinding raw materials and/or use of large volumes of toxic and environmentally hazardous leaching solutions, in particular, cyanide. Marianist the e leachate solutions on the basis of acid and hypochlorite are not selective and along with the dissolution of gold was transferred to the solution of a large amount of iron. There are losses of gold during its adsorption on iron compounds, for example, the hydroxides. In addition, hypochlorite acid leaching solution to extract gold is not stable, have a tendency to rapid decomposition with the release of chlorine that are ecologically dangerous and leads to additional costs. Sodium hypochlorite is stable at room temperature in alkaline solutions and unstable in solutions of mineral acids. So be prepared in advance leaching the sodium hypochlorite solution in sulfuric acid, as proposed in the known methods, it is impossible due to the rapid excretion of gaseous chlorine and chlorine monoxide. Autoclave methods difficult to implement, they require equipment with high pressure and/or high temperature, with stirring, with cavitation and so on, it is difficult manageable in continuous processes. Grinding the ore to a high dispersion required for opening refractory ores require different grinding operations with high energy consumption and the use of special equipment that reduces the profitability of processing.

The technical result achieved by the invention is to improve the efficiency of complex processing of metal mineral raw materials, in particular, industrial metal-containing waste (SW), including waste metallurgies is their productions, by providing the selectivity of the extraction of iron, precious and non-ferrous metals in a single technological cycle without the high dispersion of the grinding raw materials at lower costs and emissions of harmful gases. The technical result is achieved because of the crushed raw material to form a stack, which is pretreated by applying it separately or in a mixture of solutions of surface-active agents and sodium hypochlorite. Then stack process leach solution, which is obtained by mixing the volume of the pile when applying it separately or in a mixture of solutions containing bleach, a surfactant and a mineral acid. In the leaching solution is a mixture of mineral acids or sequentially input of mineral acid. Place the feeder in a stack of these solutions can not match. Metals are extracted from the received stack productive solution. The result is an increase in the degree of extraction of metals, reduction of time of leaching, lower costs and environmentally harmful emissions.

The method is as follows. The proposed method raw materials (waste metallurgy and others) is crushed, for example, to a particle size of -10+0 mm and then made the filling of the pile. After crushing can separate the fine fraction, for example, the class -2+0 mm, to the which then separately processed, for example, agitation leaching. For pre-treatment of raw materials in the pile impose solutions of surfactants and sodium hypochlorite, for example, first in the stack serves the surfactant solution, and then the hypochlorite solution, or in the stack serves a mixture of surfactant solutions and hypochlorite, adjusting their mass content for specific recyclable materials. The surfactant solution may contain one or more surfactants, for example, sulfinol, polyacrylamide. Leach solution obtained by mixing in the volume of the pile when applying it separately and alternately aqueous solutions containing hypochlorite, surfactants and/or mineral acid. In the leaching solution can be used a mixture of mineral acids or sequentially input of mineral acid. Designated filing solutions in the stack may not be the same. Metals are extracted from the received stack productive solution. During pre-processing stacks of surfactants and hypochlorite happen interrelated and mutually reinforcing effects: reduction of surface adsorption energy (Rebinder effect), and activation of the surface of the pieces of raw materials, the emergence of multiple centers of activation, including interphase boundaries, inclusions, removal of surface films, the increase in the effective surface of the particles (pieces) raw materials. The result is effectively wetted surface RL of the Cove of the processed raw material and is moving away from the jet stream of a solution to a thin film. There is a development of existing cracks and the emergence of new micro-cracks in the pieces of raw material. Surfactants and active chlorine from the solution are sorbed on the free surfaces, primarily on the surface of the cracks, including the newly formed, thus providing the strengthening of the "wedging effect". Therefore, pre-treatment enhances the cracks in the particles of raw materials, ensuring the penetration of a solution containing hypochlorite, in existing and new microcracks, pores of the particles of the raw material, thereby preparing them to leaching. During the hydrolysis of hypochlorite are allocated chlorine, oxygen and formed hypochlorous NOS and hydrochloric acid HCl, what is already certain acidic environment. Additional process - the generation of hydrogen chloride at chain reaction

H2+Cl-=HCl+H+N++Cl2=HCl+Cl+N2+Cl-=HCl+H+etc.

This generated hydrogen chloride forms a film of a solution of diluted hydrochloric acid, accelerating the destruction of carbonates and sulphates in raw materials with the formation of soluble chlorides, which allows you to destroy carbonates and sulfates in raw materials and further expands the micro pores and helps prevent them from clogging calcium sulfate. Cleans and decollette then the leaching filled their small particles, which facilitates leaching. Sol is owned by the acid destroys the sulfides of the metals, for example, iron and zinc, present in the waste electrical and metallurgical production, putting them in the solution is: 2HCl+FeS=FeCl2+H2S

But hydrogen is highly soluble in a solution having a greater effective surface on the particles in the sample, and is oxidized to sulfur by oxygen solution:

2H2S+O2=2S+2H2O.

During the development of the particles of the raw material of microcracks filled first surfactant and bleach, and then leaching solution, in addition to happen: their gradual disclosure, reducing the strength of the particles, their further destruction due to weight of overlying layers of material. This further improves the leaching of metals. After pre-processing of the pile leaching solution containing hypochlorite, surfactant and/or acid, fills in the cracks and pores of the particles of the raw material, which surface is already covered with a thin layer of surfactant and already activated. While chlorine that is released in the decomposition of hypochlorite, actively absorbed by the developed surface film of solution covering the particles of raw material in the mass of the pile. This is due to the fact that the effective surface of the particles of raw material in the sample by several orders of magnitude greater than the geometric surface of the pile. Thus, the volume of the pile occurs and is supported by a dynamic equilibrium: "the exit of gas from the solution and its absorption is astorm with recycling of hypochlorite in solution". The probability of exit gas from the stack is small. This results in reduced consumption of hypochlorite, chlorine loss, its emission into the atmosphere. The introduction of hypochlorite solution directly into the volume of the pile, for example, to a depth of 0.1-0.25 m below the surface of the pile, is the use of a special way of the perforated pipe. As a result, the exit gases into the air above the surface of the stack is minimized. Released gas is re-dissolved in the film of fluid flow over the surface of the particles of raw material in the pile, and enjoys deep. Due to this intensifying leaching, reducing the likelihood of gas clogging of the pore space of the particles of raw material micropezidae gas. In addition, carbonate structures are subjected to decomposition into solution in the form of salts. The process occurs in the surface wetting of the particles of the raw material, which is a characteristic of the internal volume of the array of the pile subjected to leaching and surface of the pile. It is promoted as an advanced fractal surface of the particles, and significant resultant surface of the pile, both external and especially internal (inside the pile, which is many orders of magnitude higher than the surface of the array, calculated from simple geometric considerations. The leaching processes are in a sufficiently thin film of 0.05-2 mm) solution, in fact, just wetting the developed surface of the particles, eliminating the appearance of "Nesmachniy particles. As a result leach solution ratio of surface area/volume by several orders of magnitude (at least by 3-4 orders of magnitude) exceeds the value of this same relationship for large reactors. This leads to a sharp increase in the role of diffusion and surface processes of extraction and absorption of the gaseous products passing reactions, helping to accelerate the development of microcracks, their further expansion, the opening of the resistant structure of the particles of raw material. In addition, the weight of the overlying layers of the raw material in the sample leads to the growth of cracks in the pieces of raw materials, developing in the pre-treatment process, and directly in the leaching process. Thus these effects together and additionally contribute to the opening of the raw material and the extraction of metals, which in this way from the get productive solution is carried out by known methods, such as electrolytic or hydroxide precipitation, cementation on iron scrap or iron powder, deposition of gold on powder zinc or gold sorption of active charcoal. These processes of extraction of metals can go when using a leach solution containing one mineral acid. If widelycited the second solution contains several sequentially exchangeable mineral acids, the metals are extracted by the known methods of each acid. In the processing of raw materials containing gold, after pre-processing is filing leach solution containing an oxidant. Thus leach metals in the pregnant solution, which are then retrieved. To optimize the extraction of metals leaching solution can contain multiple input and sequentially successive mineral acids. Thus, after pre-treatment leaching solution is extracted non-ferrous metals (zinc, copper and others) and iron concentrations are 3-5 orders of magnitude higher than the concentration of gold. In the result of addition obtained a number of positive effects: increased concentration of gold in the treated raw materials, developing a system of cracks and pores in the exposed particles of the raw material, which together greatly facilitates the extraction of gold. In addition, preliminary extraction of substantial amounts of iron dramatically reduces unproductive loss of gold during its adsorption on iron compounds, characteristic of the known methods. The method allows to extract the metals from the SW and ores, including gold.

Examples of specific performance.

Example 1. Processing of the solid residue formed during the neutralization of waste galvanizes the production - "galvanic sludge". The feedstock (original composition in table 1) is a dense stone-like material with a hardness not less than 25 MPa. He crushed to a nominal size of 0.5 mm. Weighed 20 kg were placed in a vertical column representing the heap leaching process. The surface is crushed galvanic sludge was watered with 15% hydrochloric acid solution (without added oxidant and surfactant) for 20 hours at a flow rate of 10 l/hour. After leaching the resulting cake was filtered and the residual composition was determined microroentgens elemental analysis by scanning electron microscope "KarlZeiss", equipped with energy dispersive console. The result is in table 1.

Example 2. The raw materials, conditions and equipment as in example 1. Pre-surface crushed galvanic sludge was watered with an aqueous solution containing sulfinol (1 g/l) and sodium hypochlorite (20 g/l) for 10 hours. Then, we processed leaching solution: 15% hydrochloric acid, sodium hypochlorite (20 g/l), sulfinol (1 g/l) for 20 hours. The elemental composition of the original galvanic sludge and obtained after processing of mineral powder are shown in table 1.

Table 1.
Elemental status is in galvanic sludge and mineral powder, derived from the extraction of metals.
Wt.%AboutMgAlSiKFeCZnSnNiPb
The original sludge7,210,31,51,511,12,96,421,39,51,521,75,1
The processing example 1.15,119,50,81,9of 17.51,33,55,13,70,97,91,5
The processing example 2.26,1 46,10,42,522,30,21,80,150,170,110,080,09

Particles of mineral powder after processing galvanic sludge have a developed system of microcracks, pores and easier grinding and separation with subsequent fractionation. Its composition is close to the aluminosilicates consisting of oxides of aluminum, silicon, solid materials and can be effectively used in construction, including road, as a solid filler with a high specific surface area.

Example 3. Recycling old clinker - waste electrical and metallurgical zinc production OJSC "Electrozinc" (Vladikavkaz). The composition of the clinker given in table 2.

Table 2.
The composition of the clinker at the site (according to OJSC "Electrozinc")
Zn %Cu %Pb %Fe %Au g/tAg g/t SiO2%CaO %Al2O3MqO %S %With %
0,8-1,60,7-10,3-0,825-280,6-0,840-20031-334-61,4-1,61-1,32-41-1-15

From the original clinker after crushing stood magnetic fraction which was subjected to screening with the separation into fractions by size: -2+0 and -10+2 mm, Their composition is given in table 3.

Table 3.
The fractions clinker
DescriptionThe contents of the designated item %
FeAlZnCuSiO2
The original clinker23,9 1,881,490,972,91
Magnetic fraction -2+032,51,120,550,413,30
Magnetic fraction -10+223,12,490,940,543,61

Leaching magnetic clinker fraction spent in the columns of Plexiglas (working height 475 mm, diameter 52 mm) at 18-22°C. Pre-weighed samples of the magnetic fraction of clinker covered with the seal in the column and was applied from above through irrigation nozzles solutions, controlling the flow rate on the flow through the measuring cylinder filling for 1-5 minutes. The ratio of the volume of leach solution to the sample mass in the loop was maintained at the level of W/T=4-7. The pregnant solution is collected in the receiving tank from which after each cycle were used to select the sample for analysis on the concentration of free H2SO4and metals. After measuring the volume and adjust the content of acid in the solution by adding a calculated quantity of concentrated H2SO4and water to 4%productive RA the solution was applied on the next cycle of leaching. The content of major elements in the solutions was determined by atomic absorption spectroscopy (AAS) to install QUANTUM-2A (Fe, Al, Zn, Cu) and atomic emission method with inductively coupled plasma Analyst-400 (Si-spectrophotometry). Table 4 shows the extraction of iron in a productive solution for different numbers of cycles of leaching column. Option a - leaching magnetic clinker fraction (4% solution of sulfuric acid), option In - process clinker surfactant solution (on the basis of sulfinol) leaching 4% solution of sulfuric acid. The kinetics of leaching shows the increase in the rate of metal extraction from the clinker according to the proposed method.

Table 4.
The extraction of iron in a productive solution for options a and B.
No. of cyclesThe degree of extraction of iron, %
AndIn
15,96,5
29,0to 12.0
311,0 19,5
411,527,0
5of 17.029,0
620,033,0
1230,5-

The composition of the productive solution after cycle 7 are given in table 5.

Table 5.
The composition of the productive solution (cycle 7)
cycleH2SO4free., g/lThe contents of the designated item, g/l
FeAlZnCuSiO2
723,046,25,03,51,1632,5

In a productive solution formed noted the e gel, silicic acid, which can be selected together with iron known methods as an intermediate.

Example 4.

Has been the treatment of clinker different model solutions to validate their actions and no losses of precious metals at different treatment options clinker. Leaching solution I was prepared by dissolving 10% H2SO4in distilled water until the content of 4.0% H2SO4according to the potentiometric titration. Solution II was prepared by adding 10% H2SO4with stirring to the sodium hypochlorite solution with the initial content of 74 g/l of active chlorine until the first bubbles of chlorine. Then the solution is diluted with water to a content of 11 g/l of active chlorine. According to the potentiometric determination in the original solution contained 3.72 mol/l NaOH. The solutions additionally injected 3.0 mg/l of gold in the form soloconsolidation acid and controlled the content of gold in solution by the method of the AAS. Over time the resulting solution was decontrols and filtered through a paper filter. In the filtrates was determined by the content of Au, Ag, Fe, Cu, Zn, Al, Si by atomic absorption spectroscopy (AAS). Measurement error does not exceed ±5%. The original gold content in model solutions was 3 mg/l, the silver came in the solution of the original clinker in the process you is aleciane. All the gold in the original solution I in a short time (1 hour) interacts with the clinker, as mineral sorbent, and completely precipitated from solution to the solid phase. In the leaching process clinker solution II with the content of 11 g/l of active chlorine gold with an initial concentration of 3 mg/DM almost not deposited on the solid phase within 120 hours of contact. The silver content in the leaching solution I remains constant within measurement error of about 1 mg/DM3. In solution II, the concentration of Ag was increased from 5.2 mg/DM for 1 hour to 13.0 mg/DM3for 120 hours.

Thus, we can conclude that the solution II with sodium hypochlorite content of 11 g/l of active chlorine ensures the stability of the extraction of Au and Ag, while the sulfate system is not suitable for the extraction of noble metals and can't block their losses in the leaching process.

Example 5. Has been the treatment of clinker (example 3) within 120 hours with solutions of different options in order to determine the recovery of metals. Options: A1 - with the introduction of processed clinker solution of 4% H2SO4, A2 - leaching clinker only sodium hypochlorite solution with a content of 11 g/l of active chlorine. Table 6 shows the results of composition analysis of the original clinker and solid statcompiler processing according to different variants, as in table 7, the degree of extraction of elements.

2,6
Table 6.
The content of elements in the original sample of clinker and solid residues after processing of clinker.
Solid productsThe content of macro -,%
FeCuZnAlSi
The original clinker282,63,41,631
The solid product after processing by A190,30,22,550
The solid product after processing by A2280,40,233

Table 7.
Removing elements in the processing of clinker for 120 hours.
Treatment optionsExtraction into solution
FeCuZnAlSi
A180929754
A259560,4

Example 6. Has been the treatment of (A3) clinker (composition according to example 3) within 120 hours successively with solutions of mineral acids: sulfuric (4%), nitrogen (2%) and the hypochlorite solution with a content of 11 g/l of active chlorine containing hypochlorous acid (HClO), as the hydrolysis product of hypochlorite. Table 8-the degree of extraction of elements.

Table 8.
Removing elements in the processing of clinker for 120 hours.
Treatment optionExtraction into solution, %
AuAgFeCuZnAlSi
A371,569,78794,598,777,7

It is seen that in this way the degree of extraction of clinker metals increases.

Example 7. Has been the treatment of clinker (example 3) by the proposed method. Table 9 shows data measured gas concentration at different distances from the source of emissions. Measurement of concentrations of gases was carried out by the device "OLE 2".

Table 9.
The emission of harmful gases into the atmosphere when heap leaching clinker
IU is the sampling Concentration, mg/m cube (%)
H2SCO2SO2
L=1 m from the source (the Experiments were conducted on a column ⌀=190 mm, h=1.35 m)00,512
--"--00,1310
--"--00,1317
--"--00,1211
--"--00,24
--"--00,1711
L=2 m from the source00,512
--"--00,0517
--"-- 0011
--"--00,14
--"--00,0911

It is seen that the concentration of H2S and SO2inflated only at a distance of 1 m And they are used in heap leaching did not change in time, therefore do not depend on the initial concentration of the reactant and heavy metals in the pregnant solution. This is well explained above considerations from the point of view of the existence of dynamic equilibrium in different physico-chemical processes of generation, absorption and desorption, the interaction of gases with each other and with components of clinker, which leads to quite effective their mutual neutralization. At the same time rastvorennye H2's missing, and the concentration of other gases, as a rule, much smaller than in the column. Emissions of carbon dioxide due to reaction of acids with carbonates, as their remains in the clinker, and carbonates, gradually formed during long-term storage of clinker under the open sky. Therefore, the emission of carbon dioxide is small. Output SO2practically does not depend on time and type of process is and is determined mainly by the desorption of the branched structure of particles of clinker, film-coated leach solution, and SO2is the solution of chemical equilibrium. When dissolved in water sulfur dioxide forms sulfurous acid. While sera from 4-valent becomes 6-valent, and sulfurous acid is easily oxidized into sulfuric acid by the oxygen present in the solution:

2H2SO3+O2=2H2SO4

The resulting H2SO4further involved in the leaching of clinker. In addition, when the acid treatment of metallic iron contained in the clinker, results in the release of hydrogen ions, representing a strong reducing agent. They participate in redox reactions, but most of the hydrogen ions form molecular hydrogen, which is rapidly desorbed from the solution, and then, due to its lightness, escapes from an array of clinker. Due to its lightness it does not accumulate, and flies into the upper atmosphere, so that the formation of explosive concentrations when KB excluded. Thus, the processing of clinker by the present method does not provide significant emission of harmful gases. Experimental data indicate a fairly complete mutual neutralization of gaseous products of leaching.

1. The method of extraction of metals from ores and industrial wastes, including what would be shredded, its dumping in the form of a pile, pre-processing of raw materials in the sample aqueous solution, post-processing of raw materials in the pile leaching solution, dissolution of metals and getting productive solution with the extraction of metals, wherein the pre-processing of raw materials in the sample produce a flow in the stack separately or in a mixture of solutions containing surfactant and bleach, and the subsequent processing of raw materials in the pile leaching solution is performed by applying the solution of a mineral acid, or a mixture of mineral acid, or a solution obtained by mixing volume of the pile when applying it separately or in a mixture of solvents, containing mineral acid, hypochlorite and surfactant.

2. The method according to claim 1, characterized in that the pre-treatment is carried out consistent flow in the stack of solutions of surface-active agents and sodium hypochlorite.

3. The method according to claim 1, characterized in that the pre-treatment is carried out with a mixture of surfactant solutions and hypochlorite.

4. The method according to claim 1, characterized in that the leaching requires a solution of a mixture of mineral acids or gradually introduce the solutions of mineral acids.

5. The method according to claim 1, characterized in that solutions served in the volume of the pile in divergent places is.



 

Same patents:

FIELD: mining.

SUBSTANCE: method of bath-well leaching of metals from ores includes treatment of mineral mass by solution of leaching in baths and metal winning from product solution. Baths are formed along leached mass, in the baths bottom a system of injection and extraction wells is built located above the level of bath with depth not less than the lower point of leached layer of mineral mass, and baths are filled with agglomerated mineral mass or pulp prepared in advance from extracted material, mineral mass in baths is treated by solution of leaching, and metal is extracted from product solution. Reusable solution obtained after metal extraction is strengthened or replaced with solution of another composition and is supplied to the system of injection wells for leaching of lower layers of material, then working solution is pumped off with leached metal through the system of extraction wells and metal is extracted from it; for leaching of lower layers of material solutions of environmentally safe chemicals, such as chlorides or thiosulfates, are used.

EFFECT: invention allows improving metal extraction efficiency.

FIELD: mining.

SUBSTANCE: method for leaching of precious metals from technogenic raw material involves preparation of open working-out or capacity, waterproofing of its walls and bottom, arrangement of mineral mass in it, supply of a leaching solution, proper leaching and extraction of precious metals. The invented method differs by the fact that arrangement of mineral mass is preceded with construction in the working-out or the capacity of a system of pumping-in and pumping-out pipes perforated in lower part at the level of a future root system of plants, and after mineral mass is arranged, seeds of young plants are planted in its upper layer, which are capable of accumulating precious metals in their tissues; supply and removal of the leaching solution is performed through the system of pumping-in and pumping-out pipes after the stage of active formation of plant root system; at that, as leaching solution, active low concentrated leaching solution is used, which has passed photoelectrochemical treatment, and extraction of precious metals is performed by sorption or electric sorption of its diluted forms from pumped-out solutions and its extraction from plants extracted from mineral mass when they each a certain size.

EFFECT: invention allows improving the extraction of useful components.

4 cl

FIELD: mining.

SUBSTANCE: deposit development method using underground solution involves the following stages at which: pressure pipeline is provided, which is passed to mineral deposit containing the required mineral; at that, pressure pipeline is provided with possibility of supplying the discharged fluid to mineral deposit in order to dilute the necessary mineral and to form the extracted brine; extraction pipeline is provided, which is passed to mineral deposit and provided with possibility of supplying the extracted brine to the ground surface; discharged fluid is pumped to pressure pipeline; extracted brine is cooled during its transportation through the supply pipeline and one or more heat exchangers to separation plant; at that, cooling of the extracted brine leads to deposition of the necessary mineral, and thus formation of pulp consisting of solid crystals of the necessary mineral, which are suspended in brine; solid crystals of the necessary mineral are separated from brine in separation plant, thus forming the flow of depleted liquid brine and extracting the product in the form of solid crystals of mineral; depleted brine is transported through one or more heat exchangers to pressure pipeline; at that, discharged fluid contains the above depleted brine, and by performing the heat exchange between extracted brine and depleted brine in one or more heat exchangers in order to cool down the extracted brine and heat the depleted brine; at that, mineral crystallisation to the product in the form of solid crystals is performed due to temperature decrease of extracted brine, which takes place in the section between mineral deposit and separation plant due to heat removal from extracted brine; at that, heat removal from extracted brine is mainly performed due to heat transfer from extracted brine to depleted brine in one or more heat exchangers and heat dissipation from extracted brine to atmosphere when the extracted brine is being transported in extraction pipeline, one ore more heat exchangers and transfer pipeline to separation plant.

EFFECT: invention allows improving leaching efficiency.

21 cl, 3 dwg

FIELD: metallurgy.

SUBSTANCE: method includes drying of an industrial massif of stale tailings of upstream impoundments. Then the thickness of tailings is divided into non-productive strata including lean tailings from the upper part of the industrial massif, not exposed to hypergene changes, and productive strata from the base of the industrial massif enriched with gold and formed in the process of hypergene conversion. Then the circuit of the hypergene converted stratum is established. Afterwards tailings of upper non-productive strata are removed, and tailings of hypergene converted strata are processed. Processing is carried out by leaching with gold extraction. Gold extraction from tailings of hypergene converted productive strata is carried out with cyanidation.

EFFECT: invention provides for growth of gold production in sufficiently short periods due to simplified process cycle and reduction of time for preparation of secondary raw materials for processing.

3 cl, 1 tbl, 1 ex

FIELD: metallurgy.

SUBSTANCE: method involves construction of leakproof bottom, formation of ore pile on it, erection of sprinkling and drainage system, and in case of underground leaching - construction of pumping-in and pumping-out openings in ore deposit place; sprinkling of ore pile or supply to pumping-in openings of leaching reagent containing acid solution or acid solution in presence of reducing agent, so that production solutions containing nickel, cobalt, iron, aluminium and magnesium are obtained; their processing with extraction of nickel and cobalt; reinforcement of mother solutions with leaching reagent and their return for leaching. As leaching reagent there used are products of incomplete sulphur oxidation, which are supplied in the quantity sufficient for transition and maintenance of nickel and cobalt in the solution, as well as conversion of Fe3+ ions to Fe2+ in production solution, the pH value of which is maintained at the interval of values of 1.5-4.5, oxidation-reduction potential value is not more than 350 mV; at that, extraction of nickel and cobalt is performed using sorption, extraction and deposition methods with further reclamation of waste ore pile and reusable solutions or underground water involved in recycling.

EFFECT: increasing complete combustion of powder charges and efficiency of action of charges; increasing efficiency of extraction of nickel and cobalt; reducing consumption of acid and simplifying the flow diagram.

18 cl, 4 tbl, 4 ex

FIELD: oil and gas production.

SUBSTANCE: proposed device comprises water feed tube with bottom head Note here that the latter features length exceeding radius of reservoir and is made of flexible water feed tube furnished with mechanical muscles secured thereto and pneumatically or hydraulically communicated with pressure source to control every muscle for positioning tube end in space.

EFFECT: higher efficiency.

3 dwg

FIELD: mining.

SUBSTANCE: method for cleaning-up of ore bed reservoirs is performed by means of desalination. In this respect, hole-drilling of solid ore is performed, as well as its explosive rupture, filling of blasted capacity with working solution and egress of product solution. Besides, the outer configuration of blasted capacity is drilled around at an angle equal to slope angle of working ledge. Along the centre line of blasted capacity all the way down the cleaning-up of ore bed an efficient well is drilled. The rest of ore body is drilled around by closed parallel rows of vertical wells. While stable roach is being blasted, all the capacity of blasted ore bed, including its outside configuration, is drilled around by vertical wells of the similar depth.

EFFECT: ensuring stability of open pit side and rising safety level of mining operations.

3 dwg

FIELD: mining.

SUBSTANCE: method for heap leaching of copper-zinc ores includes irrigation of material with mine waters, gathering of productive solution. Irrigation of material is performed by means of mine water, which has undergone electrochemical treatment with preliminary addition of the salt NaCl in amount of 1-20 g/l and after treatment is characterised by the following data: the value of pH - within 2-8; oxidation-reduction potential (ORP) - 600÷1200 mV; active chlorine ionic density - 50÷3000 mg/l; oxygen density - 15÷32 mg/l.

EFFECT: invention enables to raise effectivity of leaching and extraction of copper and zinc from ore material and to reduce the cost of finished product.

FIELD: metallurgy.

SUBSTANCE: method involves disintegration, heat treatment, leaching and precipitation of vanadium compounds. The slag is ground to a particle size from - 0.2 to - 0.3 mm, vanadium and other metals are transferred from the slag into a solution of sulphates of metals using the heat of exothermic chemical reactions, "vanadium slag - sulfuric acid aqueous solution," which is conducted at temperatures ranging from 75 to 85 °C, achieved by changing the acid concentration from 20 to 30% in proportion to the size of the leaching slag particles. Vanadium and other metals are precipitated as hydroxides by treating a sulphate solution with magnesium oxide at a ratio of MgO:H2SO4 from 1:2.6 to 1:2.7 and pH 10.0÷10.4 for reactions such as: MeSO4 + MgO + H2O → Me(OH)2 ↓ +MgSO4, (1) with a turnover of magnesium reagents in the interaction of MgSO4 with NaOH: MgSO4 + 2NaOH → Mg(OH)2 ↓ +Na2SO, (2) with a possibility of exchange of MgO in (1) Mg(OH)2 by (3): MeSO4 + Mg(OH)2 → Me(OH)2 ↓ +MgSO4, (3) using the reaction: Na2SO4+Ca(OH)2 ("lime milk")→2Na(OH)+CaSO4·2H2O (gypsum)↓, for turnover of the reagents of sodium and utilisation of gypsum obtained in the form of gypsum concrete, alabaster.

EFFECT: decrease in power consumption.

1 tbl, 1 ex

FIELD: mining.

SUBSTANCE: leaching component includes ore stock pile with surface spraying device, channel for collection of productive solutions with external berm, bed of solid waterproof film located under ore stock pile, as well as at the bottom, slopes and berm of the channel. External berm width is at least three times deeper than background seasonal melting of soils. Film bed edge is embedded in central part of berm through the value which is lower than depth of background seasonal melting of soils. The proposed design of the heap leaching component prevents leaks of productive solutions in case waterproof film is broken at stock pile bottom due to waterproof barrier made of film from above and waterproof frozen soils from below. Berm surface is covered with heat-insulating material during warm season. Upper part and external slope of berm are free from snow cover during cold season. Heat-insulating material is located under film bed at the bottom and channel slope opposite to stock pile and berm surface during warm season.

EFFECT: reducing environmental and economic risk of using heap leaching plants in permafrost zone, and reducing heat loss with productive solutions.

5 cl, 4 dwg

FIELD: mining.

SUBSTANCE: method of bath-well leaching of metals from ores includes treatment of mineral mass by solution of leaching in baths and metal winning from product solution. Baths are formed along leached mass, in the baths bottom a system of injection and extraction wells is built located above the level of bath with depth not less than the lower point of leached layer of mineral mass, and baths are filled with agglomerated mineral mass or pulp prepared in advance from extracted material, mineral mass in baths is treated by solution of leaching, and metal is extracted from product solution. Reusable solution obtained after metal extraction is strengthened or replaced with solution of another composition and is supplied to the system of injection wells for leaching of lower layers of material, then working solution is pumped off with leached metal through the system of extraction wells and metal is extracted from it; for leaching of lower layers of material solutions of environmentally safe chemicals, such as chlorides or thiosulfates, are used.

EFFECT: invention allows improving metal extraction efficiency.

FIELD: metallurgy.

SUBSTANCE: invention can be used in the technology of obtaining the compounds of rare-earth metals at complex processing of apatites, and namely for obtaining of concentrate of rare-earth metals (REM) from phosphogypsum. Method involves sorption of rare-earth metals. At that, prior to sorption, phosphogypsum is crushed in water so that pulp is obtained in the ratio Solid : Liquid=1:(5-10). Sorption is performed by introducing to the obtained pulp of sorbent containing sulphate and phosphate functional groups, at the ratio of Solid : Sorbent=1:(5-10) and mixing during 3-6 h.

EFFECT: increasing REM extraction degree to finished product.

5 tbl, 5 ex

FIELD: metallurgy.

SUBSTANCE: method involves leaching of cadmium from raw material in solution of sodium ethylene diamine tetraacetate with its further extraction from solution and regeneration of ethylene diamine tetraacetate. Cadmium leaching is performed in two stages. The solution obtained at the first stage is supplied for extraction of cadmium, and residue of the first stage is supplied to the second cadmium leaching stage. The solution obtained at the second stage is used for leaching of cadmium from raw material at the first stage. Besides, leaching at the second stage is performed in presence of hydrogen peroxide at maintaining its concentration in the range of 10-15 g/dm3 during 2-2.5 hours.

EFFECT: increasing cadmium extraction degree.

2 tbl, 2 ex

FIELD: metallurgy.

SUBSTANCE: method includes joint leaching and activation of raw materials in a cage mill with extraction of metals into a solution simultaneously with crystal damage. After leaching and activation in a cage mill the material is laid into stacks, piles or trenches, treated with a solution of sulphuric acid. After treatment with a solution of sulphuric acid the material is washed with water, afterwards leaching is carried out with solutions of reagents. At the same time treatment of the material in stacks, piles or trenches is carried out with a solution of sulphuric acid with concentration of 10-30 g/l. Leaching of the material in stacks, piles or trenches is carried out with a solution of a sodium sulfide trioxosulfate with concentration of 10-20 g/l.

EFFECT: higher efficiency of metals extraction from mill tailings due to additional chemical treatment of mechanically chemically activated structural components of extracted materials after their extraction in a cage mill.

3 cl, 4 tbl, 1 ex

FIELD: metallurgy.

SUBSTANCE: method includes joint leaching and activation of raw materials in a cage mill with extraction of metals into a solution simultaneously with crystal damage. Prior to supply of raw materials into the cage mill, it in the mixture with elemental sulphur is previously treated with a solution of a mixture of sulphuric and nitric acids. Raw materials are mill tailings in the form of a pulp at the weight ratio of a solid phase to a liquid phase equal to 1:2. At the same time they are ground in the mixture with elemental sulphur in the amount of 12% relative to the mass of tailings to the size of 100% - 0.01 mm. Pulp treatment with a mixture of sulphuric and nitric acids is carried out at the weight ratio of the latter equal to 2:1 to bring the hydrogen index pH to the value of 1 with its further increase to the value 3 for 2 hours.

EFFECT: higher efficiency of metals extraction from mill tailings due to increased chemical activity of the latter.

2 cl, 1 ex

FIELD: metallurgy.

SUBSTANCE: method includes leaching of useful components from open grains of processed raw materials in a cage mill, when loading raw materials and leaching reagent simultaneously in it. Raw materials processed in the cage mill are additionally exposed to vibration in the horizontal plane with its tossing. At the same time exposure to vibration is carried out within the frequency of oscillations from 30 to 1500 Hz at amplitude of horizontal oscillations from 2 to 50 mm and amplitude of vertical tosses of up to 30 mm.

EFFECT: higher efficiency of metals extraction from mill tailings or off-grade raw materials due to considerable increase of leaching speed.

7 dwg

FIELD: metallurgy.

SUBSTANCE: invention relates to the field of hydraulic metallurgy and may find wide application in metallurgical industry. The method for complex processing of iron ore with high content of magnesium compounds consists in the fact that prior to annealing the initial ore is treated with a demagnetising acid agent. The acid agent used is an anhydrous phosphoric acid. After treatment the mixture is exposed to oxidising decarbonising annealing at the temperature of above 650°C. The produced ash is treated with 10% aqueous solution of sulphuric acid, leached with water to produce pH of 6.5-7.0 in last portions of washing water. After leaching the concentrate is separated from washing water, dried and sent for iron smelting. Washing water is treated with ammonia until complete deposition of magnesium-ammonium phosphate, which after drying is sent for making fertilisers. The remaining aqueous solution is treated with quicklime to produce calcium sulfate residue, which is then dried and sent for use as a binding material. The remaining water is returned for leaching.

EFFECT: higher content of iron in a concentrate with simultaneous controlled reduction of magnesium oxide content in it.

1 tbl

FIELD: metallurgy.

SUBSTANCE: invention relates to electrolytic production of metallic lead from sweet lead paste that makes active part lead-acid accumulator. Method comprises the following steps: a) leaching of sweet paste by bringing it in contact with solution containing ammonium chloride to obtain solution after leaching and discharge of CO2 gas; b) separation of first solid residue and first clarified solution after leaching from step (a); c) leaching solid residue separated at step (b) by bringing it in contact with solution comprising ammonium chloride and hydrogen peroxide; d) separation of second solid residue and second clarified solution after leaching from solution after leaching from step (c); e) combining first clarified solution after leaching from step (b) with second clarified solution after leaching from step (d) to produce single solution; f) electrolysis of solution from step (e) in flow-through cell at current density of 50 to 10000 A/m2. Note here that electrolysis brings about mossy lead. Invention relates also to method of desulfonation of said paste.

EFFECT: higher yield and efficiency, simplified process.

26 cl, 6 dwg, 2 ex

FIELD: metallurgy.

SUBSTANCE: invention relates to mineral stock processing and may be used for extracting gold fractions of grain size smaller than 0.07 mm. Proposed method comprises preparing water suspension with addition of flocculating agent. Damped ground paper bulk is added to said suspension, paper bulk features reduced moisture resistance and mineral component-to-bulk ratio making 1: 0.05. Then, mix is mixed in mixer for 10 s. After mixing, paper bulk is separated on sieve with mesh size not exceeding 0.2 mm. Now, paper bulk is rinsed to produce concentrate to be dried and fused.

EFFECT: higher efficiency, lower costs.

1 ex

FIELD: metallurgy.

SUBSTANCE: method involves sintering of catalyst, leaching of sinter and deposition of aluminium at the first stage and molybdenum at the second stage from the solution. Catalyst is mixed with soda solution at solid-to-liquid ratio of 1:0.8÷1 prior to sintering. Soda consumption is taken based on 200-400 kg/t of raw material. The obtained sinter is subject to water leaching during 1-2 hours at temperature of 50-80°C. At that, molybdenum is deposited in the form of calcium molybdate at the second stage.

EFFECT: increasing molybdenum extraction efficiency.

3 cl, 1 ex

FIELD: metallurgy.

SUBSTANCE: method involves agglomeration of mineral raw material, leaching of gold and further extraction of gold from the solution. Prior to leaching, fractional separation of mineral raw material is performed so that slurry fraction and the main volume of large-sized agglomerated mineral raw material is obtained. Slurry fraction is subject to photocatalytic cuvette leaching with mixed alkaline hypochlorite and hydrochloride solutions. Leaching of gold is performed from the main volume of large-sized agglomerated mineral raw material in stages using the solutions supplied through perforated pipes. Initially, leaching is performed in penetration mode using a concentrated cyanide solution. Then, after exposure period in diffusion mode, leaching is performed by supplying water and compressed air or weak solution of cyanides through perforated pipes.

EFFECT: increasing efficiency owing to improving the gold extraction and reducing the leaching time.

1 ex

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