Method of copper extraction from solutions
SUBSTANCE: method includes copper sedimentation by solution contact with copper-bearing clinker. Before sedimentation clinker is treated with solution containing sulphydric collector, for instance solution containing 0.5-10 g/l of xanthate, during 15-30 minutes. After treatment clinker is contacted with copper-bearing solution.
EFFECT: improving clinker sedimentary capacity, rate and degree of copper sedimentation.
1 tbl, 1 ex
The invention relates to non-ferrous metallurgy, in particular to methods for extracting copper from poor technological and waste solutions. In particular, the method can be used to extract copper from solutions heap or underground leaching and acid mine water.
The copper content of such solutions does not exceed 5-10 g/l, and the concentration of the free acid not more than 5 g/l (pH≥1,5-2). Apart from copper solutions contain zinc, iron and smaller amounts of other metals. When heap and in-situ leaching solutions are in circulation, and the main task is the most complete extraction of copper. The impurities thus tend to leave in solution. From acidic dilute solutions in practice most of the copper is removed by cementation, sorption, extraction (1. EN 2070587 from 20.12.96; 2. SU 312886 And from 28.10.71; 3. SU 414322 And from 05.02.74; 4. SU 456413 And from 05.03.75; 5. UK 2270088 And from 02.03.94; 6. WO 96/02679 And from 01.02.96).
Cementation is mainly carried out with the use of iron scrap or chips. When extracted from the technological solutions used metal zinc, Nickel and other metals. In any case, the resulting cemented contains a significant amount of precipitating metals, and the cost of used metals-amendatory reduce the economic efficiency of these methods.
Sorption and extraction allow polarad intermediate operations to obtain a very squared away and even refined copper, sorbents and extractants are in current use and this increases the efficiency of extraction of copper. However, the multistage technology, high cost used extracting chemicals and sorbents are the major drawbacks of these options.
The set of essential characteristics closest to the claimed may be adopted a method using copper clinker as a material for cementation of copper (7. EN 2118990 from 20.09.1998).
Clinker is an intermediate formed during the processing of zinc sulfide concentrates, contains 2.5-3% Zn, 1 to 3% Pb, 1-3% Cu, 35-40% Fe. The particle size of the clinker from dust up to 50 mm, an Essential component of the clinker is carbon (20-30%). To extract copper and precious metals often clinker processed in copper production.
The basis of the prototype is the use of organic carbon (coke, coal) and metallic iron in the clinker for the extraction of copper from solutions. On carbon with highly developed surface, copper sorbed. Iron acts as comentator. Clinker in contact with copper-bearing solutions enriched with copper and more than can be effectively processed in copper production.
Thus, the use of clinker in the processing of copper-containing solutions can solve the ve tasks to extract copper from poor solutions and enrich clinker copper.
The main disadvantage of the prototype is relatively low precipitation ability of clinker. 1 ton of a typical zinc clinker production in the regime of percolation of the solution heap leaching with initial copper content of 1.5 g/l allows you to extract no more than 20 kg of copper. However, the duration of contact of the solution and clinker - at least 20-30 minutes, and the residual equilibrium copper content of not less than 0.03-0.05 g/l
The present invention aims to eliminate this drawback and to improve the precipitation ability of clinker, the speed and extent of deposition of copper from poor solutions.
The task is solved in that the clinker pre-treated with a solution containing sulfhydryl collector, such as xanthate, and then processed clinker is brought into contact with the copper-containing solution.
Xanthate, like all sulfhydryl collectors used in flotation with iron cations and heavy non-ferrous metals forms a poorly soluble compounds. Coating the surface of the sulfide mineral particles these connections give them properties, hydrophobicity and based on this flotation. The low solubility of xanthates heavy non-ferrous metals are also used for their extraction from waste dissolve the s.
Contact clinker with a solution of xanthate (modifier solution) at the stage of preliminary processing of oxidized and hydrated the surface of the particles of metallic iron, the surface oxide is covered with a monolayer of iron xanthate:
The surface of coal particles, including pores, also covered by the xanthate due to sorption. The xanthate in the end is firmly fixed on the surface of particles of clinker.
After treatment with a solution of xanthate clinker is separated from the treatment solution and brought into contact with the copper-containing solution. Owing to the greater strength of the connection Cantat-ion battery with copper, the latter displaces iron from the surface of the connection:
A similar connection is formed also on the surface and in the pores of the carbonaceous fraction of clinker.
A feature of this process is that the mass of clinker granules concentration of precipitating reagent - xanthate is quite high, while the remainder of the reaction reagent system does not contain. This allows the reaction zone the equilibrium to shift towards the full transfer of copper in the solid phase. During percolation magisteria is his solution of the copper remains in the clinker, filtering is not required.
Conditions of pre-treatment must meet
requirements as fast as possible and complete saturation of clinker adsorbed xanthate. Experiments have shown that these requirements are met by the concentration of xanthate in the modifying solution of 0.5-10 g/l, and a duration of 15-30 minutes.
Implementation of the proposed method of analysis described in the following examples.
The clinker used for the deposition of copper had a composition of 3.5% Zn, 3%R to 2.6% Cu, 34% Fe, 22% S. Of existing clinker samples by sieving singled out a class - 10+0,25 mm as the modifier used a solution of potassium butyl xanthate in technical water.
The investigated model copper-containing solution had the composition: 130 mg/l Zn, 760 mg/l Cu, 1370 mg/l Fe; pH of 2.1.
Sample clinker weighing 100 g was brought into contact with 0.5 l of a solution of xanthate in the reaction flask. The concentration of xanthate in the modifying solution is given in the table. At the end of a specified time modified clinker were filtered off, washed free from xanthate and brought into contact with the copper-containing solution (0.5 l). The copper deposition was performed with periodic mixing and sampling of the solution. In the samples analyzed the content of copper.
For comparison, a spent copper deposition source clinker according to the method of the prototype.
Results the ATA experiments presented in the table.
|no experience||The duration of treatment xanthogenates, min||The concentration of xanthogenate in the modifying solution, g/l||The duration of the deposition of copper, min||The residual copper content, mg/l|
|7||Prototype (original clinker)||30||64|
Comparative analysis of the known technical solutions, including fashion, selected as a prototype, and an alleged invention allows to make a conclusion, Thu is exactly the set of stated characteristics are provided by the perceived achievement of the technical result. Implementation of the proposed method of analysis makes it possible to increase the degree and rate of deposition of copper from poor solutions when used as a precipitator of clinker.
The method of extracting copper from copper-bearing solutions, including deposition of copper by contacting the solution with copper clinker, wherein the clinker pre-treated with a solution of sulfhydryl collector, which is used as the xanthate solution with a concentration of 0.5 to 10 g/l, within 15-30 min, followed by contacting the treated clinker with a copper-containing solution.
SUBSTANCE: method involves treatment of rock with a sodium cyanide solution with formation of dispersion of rock particles with gold compound in the form of Na[Au(CN)2], which is dissolved in it. Then, particles are removed from the dispersion so that clarified solution of gold compound is obtained. Clarified solution contacts a solid zinc source so that their products are obtained as a result of reactions of ionic exchange and replacement in the form of water solution of zinc compound Na2[Zn(CN)4] and solid phase of gold. Solid phase of gold is separated and processed so that metal gold is obtained. As zinc source there used are particles of zinc hydroxide consisting of a composite sorbent dispersed in water, consisting of cellulose fibres with particles of zinc hydroxide, which are immobilised with them at their chemical deposition. Solid phase of gold is extracted in the form of its hydroxide.
EFFECT: accelerating and simplifying the process.
4 cl, 3 ex
SUBSTANCE: invention can be used for extraction, concentration and cleaning of molybdenum from companion elements (Fe3+, Cu2+, Zn2+, Ni2+, Co2+, Al3+, Sn4+, Sb3+, rare-earth elements3+, etc.) at processing of different liquid and solid molybdenum-containing wastes and middling products. Extraction method of molybdenum from diluted acid solutions containing companion elements of molybdenum involves molybdenum deposition in the form of its salt. Besides, deposition with molybdenum purification is performed in the form of its cesium salt of 12-molybdophosphoric acid containing the following: Cs3-xHxPMo12O40·nH2O (x=0-1, n=9-12). Deposition is performed at heating up to 40-80°C by subsequent addition of orthophosphate-ion in the form of soluble phosphate or orthophosphoric acid, strong acid, for example sulphuric acid or sodium hydroxide up to pH 1-3 and soluble cesium salt, including mother solutions obtained during leaching of pollucite.
EFFECT: increasing extraction degree of molybdenum from process and effluent solutions.
2 dwg, 3 ex
SUBSTANCE: reduction is performed with hydrogen generated in solution; at that, reduction is catalysed with reduced metal itself, which is contained in finely dispersed state. Reduction process is performed in multi-pass reactor at variable pressure that is changed with frequency of 1-5 Hz from maximum to minimum values of 8 kg/cm2 to 0.25 kg/cm2. Extraction plant of metals capable of hydrogen absorption from solutions includes dosing device, modified displacement pump, electrolyser for hydrogen generation and multi-pass reactor in the form of labyrinth.
EFFECT: simplifying the process and improving the purity of extracted metal.
10 cl, 9 dwg, 8 tbl, 4 ex
SUBSTANCE: procedure for treatment zinc containing gold-silver and/or silver-gold cakes consists of sulphuric acid leaching with aeration by air or mixture of gases oxygen-air and in filtration of pulp with production of filtrate containing compounds of zinc, copper and selenium. Selenium is cemented from filtrate with metallic copper. Pulp is filtered and there is produced copper containing selenium cake and the second filtrate. At pH 1.0÷3.0 copper is cemented from the second filtrate with addition of at least one equivalent of metallic zinc. Upon total dissolution of zinc pulp is filtered and there is produced copper containing cake and the third filtrate containing sulphate of zinc. The third filtrate is electrolysed; there is produced cathode zinc. Spent electrolyte is returned to leaching zinc containing gold-silver and/or silver/gold cake.
EFFECT: reduced consumption of sulphuric acid and water at processing zinc containing silver-gold cyanic cakes into commodity silver-gold alloy, metal zinc, metal copper and selenium-cooper product.
16 cl, 1 tbl
SUBSTANCE: here are disclosed 2 versions of fabrication of high porous silver sponge where as source of silver there are used silver salts or silver alloys successively converted into salts. The versions of the procedure consist in preparing concentrated chloride solution whereat silver salt is dissolved in accordance with its solubility at temperature of solution boiling. Salt of polyvalent metal of lead chloride at amount equal to amount of dissolved silver is introduced into prepared solution. Further, silver-lead sponge is settled with zinc. Contaminating substances and lead are removed from settled sponge which is successively washed and dried.
EFFECT: accelerated production of silver sponge due to reduced time for its sedimentation; qualitative stable high porosity of produced silver sponge.
2 cl, 1 dwg, 1 tbl, 3 ex
SUBSTANCE: procedure consists in settling silver with addition of zinc powder. Before sedimentation of silver zinc powder is preliminary activated in 1-5 % solution of HCl at temperature 80-100°C. Lead chloride at amount of 2-15 g/dm3 is added into chloride solution before sedimentation. The procedure of sedimentation consists in adding activated zinc powder to chloride solution heated to 50-60°C and in successive conditioning for forming a lead sponge and sedimentation of silver on it. After conditioning the formed sponge is broken and solution is mixed. Activated powder of zinc is added in big portions.
EFFECT: raised efficiency of chloride solution purification, increased output of silver, reduced consumption of zinc and time of sedimentation, and thereby reduced cost of process.
2 cl, 1 tbl, 3 ex
SUBSTANCE: inventions relate to gold extraction from solutions with low concentration at presence of ions of other metals, for instance cleaning solutions of gold-extracting plants, brines of potassium manufacturing, geothermal water, water of brine lakes and salt water. Essence consists in that through powder of metal-restorative it is passed gold-containing solution with low concentration at presence of ions of other metals during 2-240 hours. In the capacity of metal-restorative it is used lead-plated zinc powder of grade +0.001 mm - 2 mm with lead content 1-90 wt %. or powders of metals, used at temperature of solution not less than 50°C and selected from the group: Zn, Fe, Ni, Pb, Sn, Sb, of grade +0.1 mm - 5 mm. Additionally before cementation powders are placed in cartridge. Received after cementation gold-containing concentrate is separated by means of intensive mechanical agitation, it is treated by nitric or acetic acid. Gold sediment is separated by filtration, dried and molten with fluxing additives with receiving of crude metal.
EFFECT: increase of effectiveness and selectivity of gold extraction from solutions with low concentration.
3 cl, 1 dwg, 3 ex
FIELD: process engineering.
SUBSTANCE: invention relates to process engineering and can be used for processing antimony-based alloys containing noble metals in concentrations over 0.1%. Proposed method comprises dissolving alloys in solution containing acid and extracting noble metals from said solution by cementing. Prior to dissolving alloys, lead is remove therefrom by processing with solvent. Alloys are dissolved by solution containing hydrochloric acid and hydrogen dioxide or sodium persulphate. Noble metals are cemented by antimony-based alloys with minor concentration of noble metals or cathode antimony powder with grain size varying from 100 to 74 mcm, or by gold-antimony flotation concentrate with grain size varying from 100 to 74 mcm to produce an alloy enriched with noble metals cements noble metals. Now, noble metals are extracted from obtained products.
EFFECT: treatment of alloys with wide range of noble metal concentrations within 0,1 to 1,3 %.
4 cl, 2 tbl, 5 ex
FIELD: process engineering.
SUBSTANCE: invention relates to process engineering and can be used in gold cementation with rotary solution flow. Proposed device comprises metal cementing gadget, initial solution inlet branch pipe, solution outlet branch pipe, cementation product discharge branch pipe and vibrator with vibro drive. Device incorporates two tanks representing spiral of Archimedes and arranged one above the other around central common perforated pipe with rubber shock absorbers made on every tank. Aforesaid metal cementing gadget is arranged in baskets mounted inside said tanks. Solution discharge branch pipe is located at lower tank bottom. Basket accommodating said metal cementing gadget represents a vessel with walls perforated along solution flow, holes diameters varying from 2 mm to 3 mm. Vessels arrangement allows working solution to flow in opposite directions.
EFFECT: increased rate of cementation.
7 cl, 1 dwg
SUBSTANCE: invention relates to methods of vanadium sedimentation from water solutions and can be used in hydrometallurgy of rare refractory metals, particularly receiving of vanadium oxide (V+5) of high purity. Method of vanadium extraction from sodium-bearing solutions includes electrodialysis of solution for membrane withdrawal of sodium cation from solution and sedimentation of ammonium pol-vanadate. Electrodialysis is implemented at circulation of solution through working chamber of electrodialysis apparatus and at achievement of pH 6.5-7.5 circulating solution is treated by ammonia water or ammonia. Treatment is implemented up to molar ratio Na:V<0.1.
EFFECT: providing of intensification of sedimentation process of vanadium, improvement of finished product and elimination of discharge of industrial flows.
1 dwg, 4 ex
SUBSTANCE: method includes catalyst dilution in chlorhydric acid with palladium chloride and other metals solutions obtainment. Then three-staged treatment of solutions by sodium hydroxide with fibrillated cellulose fibres available in solution as sorbent is performed, composite materials being obtained at each stage consisting of cellulose fibres with metal insoluble compounds particles immobilised by them, at each stage composite materials are extracted by pressure flotation method.
EFFECT: simplifying process, increasing degree of palladium regeneration, utilisation of copper and aluminium and process performance in continuous mode.
5 cl, 1 dwg, 1 ex
SUBSTANCE: invention proposes a purifying method of copper or nickel alloys or copper, which contain lead and/or zinc, and is characterised by the fact that melting of the above alloy or metal is performed in a melting furnace with its overheating. The, molten metal is supplied to a vacuum chamber, from which air evacuated, vacuumised and exposed in the vacuum chamber. Then, vacuum is released and an alloy or copper billet is drawn through a crystalliser interconnected with the melting furnace. Zinc and lead impurities removed during molten metal vacuumising are supplied to a condenser, in which they are sprinkled with molten lead supplied from the bath, and lead and/or zinc billets are drawn through crystallisers interconnected with the lead and zinc bath. For vacuumising of molten metal and its exposure, the vacuum chamber is isolated from action of ambient air through a refractory layer of the chamber by separating the refractory layer at the vacuum chamber inlet into two parts, one of which is represented by a lower part located before the vacuum chamber inlet, which is permeable for atmospheric air. The second part represents an upper part of the refractory layer, which is impermeable for atmospheric layer and located in the vacuum chamber above the line located in the part of the refractory layer, in which pressure of alloy or copper is equal to or higher than atmospheric one art full vacuum. A plant for the method's implementation is proposed as well.
EFFECT: improving quality and increasing the purifying rate of alloys and metal; simplifying the plant design.
2 cl, 3 dwg
SUBSTANCE: method for processing of copper-based electronic scrap containing noble metals, consists in the fact that the electronic scrap is exposed to oxidising melting to produce an alloy with copper content of 55-85 wt %. The produced alloy is exposed to dissolution by means of electrochemical dissolution in a sulphate copper solution at voltage of 0.8-1.5 V on electrodes with production of sludge containing gold and silver, and an alloy on the cathode, containing copper and palladium. This alloy is exposed to electrochemical dissolution in the copper sulphate solution at voltage of 0.3-0.5 V on electrodes to produce copper on the cathode and sludge containing palladium. At the same time the produced sludges without mixing are leached with sulfuric acid.
EFFECT: higher extent of copper and noble metals extraction from copper-based electronic scrap.
SUBSTANCE: proposed method comprises control over copper content in matte and stabilisation of matte composition by maintaining reset melting conditions by correcting control effects. Note here that correction of said control effects is carried out continuously by compensating disturbances in discrete delayed control over copper content in matte corresponding to equivalent delay defined by mathematical expression.
EFFECT: matte quality stabilised in time and composition.
SUBSTANCE: proposed method comprises thermal treatment of residues in air whereat temperature is increased to, at least 500°C at the rate of 150 °/h and curing at said temperature for, at least, two hours. Treated residues are mixed with aluminium powder resulted from grinding aluminium chips and are subjected to aluminothermy with subsequent separation of formed alloy and slag. Aluminothermy is conducted in tight reactor with continuous discharge of gaseous and sublimate reaction products. Note here that aluminium powder and thermally treated residues are taken at the ratio of 1: 6.5-7.0).
EFFECT: higher efficience of processing galvanic process copper bearing residues, method simplifying and higher ecological safety.
3 dwg, 2 tbl, 2 ex
SUBSTANCE: said air suspension and reducing agent are placed inside isolated vessel provided with perforated branch pipe located at vessel bottom to make air suspension and communicated with external pipeline for feeding compressed air at excess pressure of 0.1-0.6 kgf/cm2. Raw stock 0.02-1.0 mm-dia particles filled some 20-40% of the volume of said vessel. Said reducing agent represents carbon-bearing compounds contained in compressed air fed to make suspension of particles inside said vessel. Said suspension and reducing agent are subjected to effects of variable rotary magnetic field with intensity in treatment zone of 1.5×103÷1×106 A/m and frequency of 40-70 Hz. Reduction brings about copper particles. Components for generation of aforesaid field are composed of interconnected plates made from permeable material and shaped to rectangle inside which three windings-coils are arranged. Every said coil is electrically connected with appropriate phase of external three-phase power supply. One of said components has through groove that allows fitting into said vessel of cover arranged atop said vessel to inhibit communication with surroundings.
EFFECT: lower costs, simplified design.
2 cl, 3 ex, 2 dwg
SUBSTANCE: 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.
EFFECT: provision of development of a wasteless technology, which ensures extraction of copper and zinc from sludges of neutralisation of acid mine waters into end products and production of an additional end product - a binder for production of construction materials.
1 dwg, 7 tbl
SUBSTANCE: proposed method comprises ore pretreatment, bulk flotation in alkaline medium at pH 11-12 to obtain copper-molybdenum concentrate. Bulk copper-molybdenum concentrate is subjected to treatment by bacteria Pseudomonas Japonica with titre of 6·107 kl/ml for 2-5 min. Then, selective flotation is performed to separate molybdenum and copper into foam product and flotation tail, respectively.
EFFECT: higher efficiency, intensified process.
1 dwg, 1 tbl
SUBSTANCE: method of extracting copper from an aqueous solution involves bringing an extractant in form of plant oil into contact with the solution. The mixture is stirred, settled and subjected to phase separation. Extraction is carried out from an aqueous solution with copper concentration ≤5 g/dm3 with ratio of the aqueous phase to the organic phase A:O≤8, pH 5.5-6.5 and 8.5-10.5, wherein pH is controlled for not more than 30 minutes.
EFFECT: high efficiency of extracting copper from aqueous solutions with simultaneous cost-effectiveness and safety of the process.
6 dwg, 6 ex
FIELD: process engineering.
SUBSTANCE: invention relates to flotation of man-made stock. Method of flotation of sulfide ores of nonferrous and noble metals comprises conditioning crushed ore with dithiophosphate solution or other sulfhydric collectors in lime medium and flotation. Note here that for reduction in floatability of pyrite and increase in extraction of metal up to 10 wt % of thiourea ((NH2)2CO) or its derivatives are preliminary introduced in the solution of dithiophosphate as a modifying agent. Then, pulp from ore is conditioned, first, with modified dithiophosphate at pH 8.5-9.0 for 3-5 minutes and, then, with, xanthate at pH over 9.0 for 1.0 minute. Then flotation of sulphides of nonferrous metals and mineral forms of noble metals at input of modified of dithiophosphate and xanthate varying from 1:3 to 3:1, respectively.
EFFECT: reduced floatability of pyrite and other iron sulphides, increased floatability of nonferrous metal minerals, native gold particles and its exposed concretions with sulphides.
3 tbl, 3 ex
FIELD: non-iron metallurgy, in particular reprocessing of copper containing sulfide materials.
SUBSTANCE: invention relates to reprocessing of copper containing materials to produce solutions useful for copper recovering. Method includes two-step autoclave leaching with sulfuric acid. The first step is carried out with limited copper converting into solution. On the second step precipitate is fully leached with fresh sulfuric acid solution while maintaining specific ratio of liquid and solid phases. Method of present invention makes in possible to produce in both leaching steps copper containing solutions of desired composition.
EFFECT: improved method for copper recovering, reduced capacity of autoclave equipment.
23 ex, 1 tbl