Method for processing of copper-based electronic scrap containing noble metals
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.
The invention relates to the metallurgy of non-ferrous metals and can be used by enterprises to obtain non-ferrous and precious metals and their alloys obtained by recycling of electronic devices and components.
A method of refining metal scrap containing copper (avts SU # 1669194, publ. 23.12.1992,), including selective smelting of copper by immersion baskets of scrap in the melt. To extract contained in the scrap refractory metals smelting lead to the solution of calcium at 850-870°C.
The downside is that cleaning copper alloy passes through the individual components. Cleaning copper is not completely.
A known method of producing alloys of copper from secondary raw materials (avts SU # 1836473, publ. 23.08.1993, including the mixing of metal-containing component with a top-refining flux, briquetting the mixture, the melting of the pellets. As a metal-containing component is used wrens metals fraction 7-0,5 mm, mixed with flux is carried out in a ratio of 1:0,02-0,04 use a flux with a melting temperature of 100-150°C below the melting temperature of the metal, and briquetting of metal leads to a density of 6.4 to 7.0 g/cm3.
The downside is that cleaning copper alloy passes through the individual components. Cleaning copper is not completely.
There is a method of refining the edit (avts SU # 1406198, publ. 30.06.1988, including the oxidation of molten copper by oxygen, reduction of oxidized copper in the molten metal by carbon or hydrogen-containing reagent and electrochemical dissolution of copper. In order to reduce the quantities passing the resulting circulating copper-containing intermediates and increase the recovery of copper in industrial metal after recovery of oxidized copper it further treated with a reagent containing silicon metal.
The disadvantage is that it cannot be recycled copper-containing waste with a high content of metal impurities.
There is a method of processing electronic scrap containing precious metals (U.S. Pat. RU # 2090633, publ. 20.09.1997 year). The method includes melting a source of raw materials to produce alloy of complex composition, containing, in particular, copper, electrolytic refining of the alloy in acid with getting mud and cuttings. Electrochemical dissolution is carried out in a solution of nitric acid with a density of from 1.1 to 1.15 g/cm3 alternating current of industrial frequency and voltage of 5-10 V At current density of 0.02-0.2 l/cm2 to obtain a solution containing Ag, Pd and non-ferrous metals and sludge containing gold and tin. The sludge carried by annealing at 500-550°C and leaching the product of calcination in Aqua Regia.
a method of refining alloys, containing precious metals on the basis of Cu and/or Zn (U.S. Pat. RU # 2017842, publ. 15.08.1994 g)adopted for the prototype. The method comprises dissolving in solutions containing HNO3and the subsequent allocation of precious metals by cementation. The dissolution of the subject alloys with noble metal content greater than 45%, and the cementation is carried alloys or with a lower content of precious metals with obtaining cement noble metals, or with a high content of noble metals with obtaining cement noble metals and alloy chementator, followed by separation of precious metals from the product received.
The disadvantage of this method is the use of nitric acid, which requires special methods of environmental protection.
The disadvantage of this method is that the alloy after melting is subjected to separation into elements using nitric acid, which requires special methods of environmental protection.
The technical result is to increase the degree of extraction of copper and precious metals from electronic scrap.
The technical result is achieved in that in the method for processing electronic scrap copper based, containing precious metals, including smelting source material with obtaining alloy electrochemical dissolution of the alloy in the solution obtained with the eating of the sludge, processing of the obtained products, electronic scrap is subjected to oxidative heat to obtain an alloy with a copper content of 55-85 wt.%, the obtained copper alloy is subjected to electrochemical dissolution in sulphate solution copper when the voltage at the electrodes of 0.8-1.5 V to obtain a slurry containing gold and silver, and an alloy containing copper and palladium, which is subjected to electrochemical dissolution of sulfate in the solution of copper, when the voltage at the electrodes of 0.3-0.5 V to produce copper and sludge containing palladium, with the resulting sludge, no mixing, leached with sulfuric acid.
Oxidative fusion to obtain an alloy with a copper content of 55-85% and the use of copper sulfate helps to ensure the possibility of electrochemical dissolution of the anode.
Electrochemical dissolution of the obtained copper alloy in sulphate solution copper when the voltage at the electrodes of 0.8-1.5 V provides and allows you to separate gold and silver from palladium and copper to obtain a slurry containing gold and silver, and an alloy containing copper and palladium.
The implementation of electrolysis at 0.8 to 1.5 In sulphate solution copper allows you to transfer to the cathode copper and palladium. The reduction in voltage below 0.8 V leads to the transition of palladium in the slurry, and the increased voltage is greater than 1.5 In the decomposition of the electrolyte.
Electrical wiring in khimicheskoi dissolution of the alloy, containing copper and palladium, in sulphate solution copper when the voltage at the electrodes of 0.3-0.5 V to produce copper and sludge containing palladium, allows to separate the copper and palladium.
The second electrolysis at a voltage of 0.3-0.5 V translates palladium in the sludge with getting on the cathode electrolytic copper.
The sludge leaching in sulfuric acid increases the concentration of noble metals in the sludge due to the removal of oxidized copper compounds.
Low boiling point of nitric acid determines the high volatility vapors HNO3. Use in the leaching of sulfuric acid instead of nitric acid provides high performance for the recovery of precious metals and environmental friendliness.
Sludge after electrochemical dissolution are concentrates of gold, silver and palladium, which can be processed by known methods
The method is as follows. Electronic scrap copper based, containing precious metals, is subjected in a known manner oxidizing smelting to obtain an alloy with a copper content of 55-85 wt.%. Smelting is carried out, for example, in an induction furnace (see Daijosai. Metallurgical furnaces, ed. "Metallurgy" M, page 612), the oxidation of the impurities is carried out, for example, fed into the melt of the air (see Nvhodgm, Apple is I. Quick reference metallurgy of non-ferrous metals, ed. "Metallurgy", M. 1975, str).
Then the obtained copper alloy with a copper content of 55-85 wt.% subjected to electrochemical dissolution of the anode in sulphate solution copper when the voltage at the electrodes of 0.8-1.5 V to obtain a slurry containing gold and silver, and alloy on the cathode containing copper and palladium. The process is carried out, for example, in the electrowinning cells (see Nvhodgm, Apini, Quick reference metallurgy of non-ferrous metals, ed. "Metallurgy", M. 1975, p.148). Obtained at this stage, the slurry containing gold and silver are leached with sulfuric acid. The leaching is carried out, for example, in the apparatus with a mixing device (see Enamel equipment. The catalogue. M Containerised, 1986).
The cathode is an alloy containing copper and palladium, is subjected to electrochemical dissolution of the anode in sulphate solution copper when the voltage at the electrodes of 0.3-0.5 In getting to the cathode copper and sludge containing palladium. The resulting slurry containing palladium, not mixing with the slurry containing gold and silver are leached with sulfuric acid.
Example 1. Electronic scrap copper based subjected to oxidative heat to the copper content of 55 wt.% (the composition of the alloy, wt.%: copper - 55,0; Nickel - 15,5; cobalt - 0.8; zinc - 15,0; lead - 2,6; olo is about - 1,5; iron - 5,2; silver - 3,5; gold - 0,20; palladium - 0,9). The resulting alloy is subjected to electrochemical dissolution in sulphate solution copper when the DC voltage on the electrodes of 1.5 In obtaining slurry containing gold and silver, and an alloy containing copper and palladium.
Of the copper alloy in the sludge passes 99.9% of gold and silver and 0.5% of palladium. The cathode goes to 99.9% copper and 99.5% of palladium. A slurry containing gold and silver are leached with sulfuric acid solution.
Obtained at the cathode alloy containing copper and palladium, is subjected to electrochemical dissolution in sulfuric acid solution of copper when the DC voltage on the tub 0,3 Century in the sludge goes to 99.9 wt.% palladium, and the cathode of 99.9 wt.% copper.
The resulting slurry containing gold and silver, the first electrochemical dissolution after leaching in sulfuric acid can be recycled by melting the gold-silver alloy (metal Dore).
A slurry containing palladium, the second electrolysis after leaching in sulfuric acid contains up to 99.9 wt.% palladium.
Example 2. Electronic scrap is subjected to oxidative heat to the copper content of 85 wt.% (the composition of the alloy wt.%: copper - 85; Nickel - 5,4; cobalt - 0,2; zinc - 1,2; lead - 0.1; tin - 0.1; iron - 0,1; silver - 6.5; gold - 0,30; palladium - 1,1.). The alloy is subjected to elec is sohimicheskim dissolution in sulphate solution copper when the DC voltage on the electrodes of 0.8 Century In the sludge goes to 99.9 wt.% gold and silver, 0.5 wt.% palladium. On the cathode moved to 99.9 wt.% copper and 99.5 wt.% palladium. Obtained at the cathode alloy containing copper and palladium, is subjected to electrochemical dissolution in sulphate solution copper when the voltage at the electrodes of 0.5 C. the slurry is transferred to 99.9 wt.% palladium, and the cathode of 99.9 wt.% copper. The cathode contains 99.9% of copper. The resulting slurry containing gold and silver, the first electrolysis after leaching in sulfuric acid can be recycled by melting the gold-silver alloy (metal Dore). A slurry containing palladium, the second electrolysis after leaching in sulfuric acid contains up to 99.9 wt.% palladium.
Thus, the method allows to increase the degree of extraction of copper and precious metals from electronic scrap copper based.
A method of processing electronic scrap copper based, containing precious metals, including the dissolution of the alloy in the solution to obtain a slurry, recycling of the products obtained, characterized in that before the dissolution of electronic scrap is subjected to oxidative heat to obtain an alloy with a copper content of 55-85 wt.%, dissolution is subjected to the resulting alloy by electrochemical dissolution in sulphate solution copper when the voltage at the electrodes of 0.8-1.5 V to obtain a slurry containing gold and silver on the cathode alloy, containing copper and palladium, which is subjected to electrochemical dissolution in sulphate solution copper when the voltage at the electrodes of 0.3-0.5 V to produce copper cathode and sludge containing palladium, with the resulting sludge without mixing leached with sulfuric acid.
SUBSTANCE: method involves dissolving wastes and subsequent electrolysis of the solution, and is characterised by that electrolysis is carried out on vibrating electrodes at current density of 0.2-0.5 A/cm2. The anode is made from anodised lead and electrolyte components are in the following ratio: 40-60 g/l sodium chloride per 20-30 g/l copper-containing ammoniate wastes. The invention enables to obtain copper powder with particle size of not more than 300 nm, oxygen content of not more than 5% and output higher than 0.031 kg/(m2·h).
EFFECT: high resistance of the copper powder to hydrogen wear in powdered compositions, high corrosion resistance of the powder, high efficiency of recycling copper-containing ammonia wastes.
SUBSTANCE: method involves electrolytic refining with dissolution of anode and transition of copper ions to the cathode. At that the electrolytic refining is accelerated by setting between the anode and the cathode of the lattice with negative potential, whose elements have protective insulation from the electrolyte.
EFFECT: reduced time of electrolytic refining, and reduction of specific electricity consumption.
2 cl, 1 dwg
SUBSTANCE: method includes welding of current lead in the form of copper-coated plates to matrix basis. At that copper coating is made by electrolytic deposition at lead plates pre-treated for the purpose of increase of their surface roughness.
EFFECT: improvement of cathode electrical properties, reduction in metal consumption and increase of service life.
SUBSTANCE: procedure consists in production of copper powder in form of cathode sediment, nickel solution and non-soluble slag concentrating sulphur and precious metals. For this purpose alloy is subjected to electro-chemical anode dissolving in water solution. Also, sulphide copper-nickel alloy in form of granules of size 0.5-5.0 mm used as bulk anode is subjected to anode dissolving. Electrolysis is performed at anode density of current 20.0-40.0 A/m2. As source alloy there is used nickel, copper-nickel matte or white matte. Sulphuric acid is used as non-organic acid.
EFFECT: increased completeness of alloy dissolving and transition of sulphur into elementary state.
4 cl, 1 tbl, 3 ex
SUBSTANCE: method includes receiving of solution for electrolysis environment and deposition of copper by electrolysis from received electrolysis with usage of steel cathode. Receiving of electrolysis environment is implemented by means of pouring of grinned ore by salt water. Electrolysis then is implemented with usage in the capacity of anode of metals and alloys, allowing in salt water electrode potential less than cathode material and not destroying during electrolysis.
EFFECT: copper extraction in ecological conditions and financial viability.
SUBSTANCE: invention refers to metallurgy, particularly to methods of electro-chemical refining of copper out of anodes with impurities of other metals. The method consists in electrolysis with anode dissolution of copper and its sedimentation on a cathode under effect of electric current with cathode density of current 220-330 A/m2. Also there is performed a direct flow circulating supply of copper containing solution with colloid and concentration of free sulphuric acid 120-180 g/dm3. Electrolysis is carried out at 50-65°C temperature of solution at rate of its circulation from 12 to 30 dcm3/min. Concentration of copper in solution is maintained within ranges 35-65 g/dcm3. Voltage in the bath during electrolysis is supported at 0.25-0.6 V at daily withdrawal of part of volume of solution from block-series of baths constituing 1-4 % from the total volume; it is made up with condensate or copper containing solution.
EFFECT: increased efficiency of electrolysis process production and upgraded quality of cathode copper of MOOK grade produced out of materials with considerable amount of impurities in raw material.
SUBSTANCE: invention is related to method for production of copper crystals with reduced specific density for correction of biophysical fields of bioobjects. Production of copper crystals is realised by electrolysis from solution of copper sulfate. Electrolysis is carried out under effect of electromagnet radiation with wave length of 9 mm and current intensity from 0.05 to 1 A and acoustic field with permanent frequency from 103 to 106 Hz.
EFFECT: creation of copper crystals with specific density that is less than average by 0,3-0,5%, which makes it possible to use them in devices of bioinformation correction.
FIELD: metallurgy, electrolysis.
SUBSTANCE: invention concerns cathode for copper receiving. Particularly it concerns hydrometallurgical receiving of starter cathodes of copper by means of electrolysis on the basis of unsupported technology. Cathode for copper receiving contains plane matrix basis made of titanium, to which by means of welding it is rigidly attached current contact jaw, containing of assembly titanium basis. On side walls of the basis there are applied plating layers of copper. Current contact jaw is implemented of trimetal copper- titanium -copper by means of explosion welding.
EFFECT: improving of electrotechnical characteristics of cathodes, reduction of its steel intensity and durability increasing which provides receiving of starter cathodes with stable characteristics, increasing of its quality, reduction of electric loss.
SUBSTANCE: method consists in electrochemical copper recovery in crystal form from univalent copper solution, in electrolytic tank, divided into cathode compartment and anode compartment, on cathode made of descending metal beads layer. The univalent copper solution being optionally contain bivalent copper chloride.
EFFECT: production of glittering coherent deposit.
12 cl, 2 ex
SUBSTANCE: invention relates to electrolysis method and to electrolytic agent used to extract metal from water solution. Method includes the stage dealing with current of non-uniform density generation along collecting surface so that sections with high current density could be generated together with low current density sections in alternating manner. Difference between high density sections and low density sections is sufficient to cause metal deposition concentrating in high density sections to facilitate non-uniform metal deposition on surface. Electrolytic agent contains cathode with collecting surface where metal is deposited during water solution electrolysis. Electric field of cathode collecting surface is not uniform. It has sections of strong electric field alternating with weak electric field sections due to creation of ordered set of alternating ridges and hollows. Ridges form strong electric field sections while hollows form weak electric field sections.
EFFECT: facilitation of metal deposition removal.
29 cl, 17 dwg
SUBSTANCE: method involves crushing chemical cells, leaching, magnetic separation and electrolysis. The cells are crushed and leached with water in an atmosphere of carbon dioxide gas without access to oxygen. Light fractions are then removed from the scrap by floatation. Filtration is then carried out. The filtrate is treated with sorbents. After filtration, the scrap is washed with water, dried and fragments of ferrous and nonferrous metals are removed by electromagnetic separation, and then leached with sulphuric acid solution. Sulphuric acid pulp is filtered through a filter with an inert material, a filter with a coal medium and a filter with a cation-exchange medium. Ions of row d and row p metals sorbed by a cation-exchange resin are selectively desorbed with sulphuric acid solutions. Solutions containing ions of row d metals are subjected to electrolysis, and solutions containing ions of row p metals are neutralised to pH 3-4 and treated with clay mineral sorbents. The precipitate after sulphuric acid leaching is leached with nitric acid solution; the undissolved manganese dioxide precipitate is removed and the filtrate is neutralised and acidified to pH 3. The precipitate is filtered off. The filtrate containing mercury ions is subjected to cathode reduction and the precipitate containing lead and silver chlorides is dissolved in nitric acid and subjected to cathode reduction in an electrolysis cell with separate deposition of metals on electrodes.
EFFECT: environmental safety of recycling any type of spent chemical cells.
SUBSTANCE: proposed composition comprises 3.0-5.0 wt % of dichlorisocyanuric acid soda as halogen-bearing compound, 0.5-1.5 wt % of thiourea as complexing agent and water making the rest.
EFFECT: higher efficiency of removal mercury from soil, reduced aggressiveness of used substances relative to rooms interior, instruments and equipment.
SUBSTANCE: proposed method comprises anodic oxidation of melt in acid electrolyte at application of electric current. Note here that said anodic oxidation is carried out in acid electrolyte containing 150 g/l of H2SO4+50 g/l HCl. Applied direct electric current features density of 250-300 mA/cm2. Application of said current is conducted at 20-40°C.
EFFECT: notable increase in anodic oxidation rate.
3 tbl, 2 ex
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: proposed method comprises blending the wastes with flux, smelting the blend, dividing melting products into slag and alloy containing copper and platinum metals. Sodium hydroxide is used as flux. Blending is carried out with copper at copper content of 80-30 wt %, flux content of 10-35 wt % and content of wastes of 10-35 wt %. Melting is conducted at 1100-1200°C for 10-20 min. Produced alloy is electrochemically dissolved in copper sulphate solution. Slag obtained in electrochemical dissolution contains platinum metals and is processed in sulfuric acid solution to remove impurities.
EFFECT: higher yield of platinum metals.
SUBSTANCE: arc-furnace dust is agglomerated together with crushed carbon reducing agent and binder material in the form of pellets. The latter are dried, heated and roasted in rotary kiln together with solid reducing agent lumps at temperature of discharged materials of 700-1000°C, gases are cooled and dust bearing zinc and lead sublimates is caught therefrom. Note here that, prior to agglomeration, arc-furnace dust is premixed with lime-bearing material and crushed carbon reducing agent in amount 1.5-2 times higher than stoichiometrically necessary content of carbon for reduction of iron, zinc and lead oxides. Mix is damped to water content of 8-11% and cured for 1-3 hours while obtained pellets are loaded into kiln together with solid carbon reducing agent lumps in amount of 200-500 kg per ton of arc-furnace dust, reducing agent lump size making 20 mm.
EFFECT: higher yield of zinc and iron metallisation.
4 cl, 2 tbl, 1 ex
SUBSTANCE: solid or melted substances are loaded on graphite body heated, at least, partially, inductively. Reducing agents are introduced therein, other than graphite carbon to collect flowing reduced and/or gasified melt. Note here that reducing agents are introduced along with solid or melted loaded particles. Said reducing agents represent natural gas, coal dust, brown coal dust, hydrocarbons, hydrogen, carbon oxide and/or ammonia to be introduced together with steam, oxygen, carbon dioxide and/or halogens or halogen hydrides.
EFFECT: simplified process.
18 cl, 5 dwg
SUBSTANCE: proposed method comprises smelting initial material to produce vitreous arsenic trisulfide. Arsenic-bearing sulfide cake is subjected to neutralisation given its moisture content does not exceed 0.5%. Smelting is performed in protective capsule preformed from liquid dump slag at 350-400°C using the heat of said dump slag. Then, buffer layer of heat-insulation material is formed on the surface of obtained cake melt. Now, said protective capsule is sealed by coating its surface with buffer layer of liquid dump slag to be hardened thereafter. Aforesaid heat-insulation layer represents crushed slag and/or quartz sand and/or undersized crushed stone.
EFFECT: higher efficiency.
2 cl, 1 tbl, 1 ex
SUBSTANCE: proposed furnace comprises body arranged at welded frame and composed of refractory outer lateral, front and rear end walls, accumulation wall and inclined platform confined by hearth and walls, crown, working and spare drain notches, working and slag opening shutters, rotary bowl and gas duct. Furnace has outer heat insulation of walls consisting of asbestos grit, dual layer of refractory mats and dual layer of asbestos cardboard sheets. Accumulation bath and inclined platform are made from corundum blocks laid on the layers of asbestos cardboard and light brick. Furnace frame is filled with concrete with filler from fireclay and asbestos grit. Crown above inclined platform and bath has heat-insulation plaster above which dual layer of refractory heat-insulation mats is laid. One lateral wall of the furnace if provided with two injection eight-mixer medium-pressure burners directed at angle to inclined platform while another lateral wall is furnished with on injection eight-mixer burner directed at angle to inclined platform and another 17-mixer reheat chamber directed to furnace hearth lined by refractory bricks to house sin-mixed gas injection burner, air blower, and waste gas heater arranged above said chamber. Notches in lateral wall for release of fused metal are made in fast-replace notch bricks.
EFFECT: higher efficiency, reduced heat losses.
7 cl, 10 dwg
SUBSTANCE: furnace includes a housing formed with side, front and rear external end refractory walls, a storage bath that is restricted with a bottom and walls, an inclined platform, an arch, a drain tap-hole and a gas duct. The housing is arranged on a welded concrete-cast frame with filler from diatomite chips and provided with two heat-insulating layers from light brick and asbestos board plates under the bottom, two heat-insulating layers from light brick and four layers of asbestos board plates under the inclined platform. The storage bath and the inclined platform are made of mullite-corundum blocks MKP-72 laid on three layers of asbestos board and have packing from diatomite chips, which are mixed with crushed asbestos chips. The furnace has lower and upper large arches located one above another so that a gap for a flue gas duct is formed between them. The furnace is equipped with a rotating chute having the possibility of being turned during liquid metal pouring and having an intermediate nose, a rotating bowl with a shaft welded in its lower part, the end of which is pressed into an inner shell of a ball bearing, and its outer shell is fixed in a bracket fixed in the rear wall of the furnace; at that, a long pouring nose with two handles is welded to the turning bowl for series pouring of metal molten in the furnace to the pouring equipment located in the service sector at an angle of 140°. Front wall of the furnace is provided with a row of injection burners of intermediate pressure, out of which two eight-mixer burners with long flame are directed on edges to the charge contained on the inclined platform and to the bath with molten metal, one burner BIGm 2-6 and two burners BIGm 2-12 are directed to the charge.
EFFECT: high furnace capacity, reduction of heat losses and melting loss and possible environmentally safe remelting of aluminium scraps.
7 cl, 5 dwg
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.