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Telyakov Alexey Nailevich. Development of an effective technology for the extraction of non-ferrous and noble metals from the waste of the radio engineering industry: dissertation ... Candidate of Technical Sciences: 05.16.02 St. Petersburg, 2007 177 p., Bibliography: p. 104-112 RSL OD, 61:07-5/4493
Introduction
Chapter 1 Literature Review 7
Chapter 2. Study of the material composition of electronic scrap 18
Chapter 3 Development of technology for averaging of electronic scrap 27
3.1. Roasting of electronic scrap 27
3.1.1. About plastics 27
3.1.2. Technological calculations for the utilization of roasting gases 29
3.1.3. Roasting electronic scrap in lack of air 32
3.1.4. Roasting electronic scrap in a tube furnace 34
3.2 Physical methods of processing electronic scrap 35
3.2.1. Description of the processing area 36
3.2.2. Technology system enrichment area 42
3.2.3. Development of enrichment technology at industrial units 43
3.2.4. Determination of the productivity of the units of the enrichment section during the processing of electronic scrap 50
3.3. Industrial testing of enrichment of electronic scrap 54
3.4. Conclusions to chapter 3 65
Chapter 4 Development of technology for processing electronic scrap concentrates . 67
4.1. Research on the processing of REL concentrates in acid solutions.. 67
4.2. Testing technology for obtaining concentrated gold and silver 68
4.2.1. Testing the technology for obtaining concentrated gold 68
4.2.2. Testing the technology for obtaining concentrated silver... 68
4.3. Laboratory research on the extraction of gold and silver REL by melting and electrolysis 69
4.4. Development of technology for the extraction of palladium from sulfuric acid solutions. 70
4.5. Conclusions to chapter 4 74
Chapter 5 Semi-industrial tests on melting and electrolysis of electronic scrap concentrates 75
5.1. Smelting of metal concentrates REL 75
5.2. Electrolysis of smelting products REL 76
5.3. Conclusions to chapter 5 81
Chapter 6 The study of the oxidation of impurities during the smelting of electronic scrap 83
6.1. Thermodynamic calculations of the oxidation of impurities REL 83
6.2. The study of the oxidation of impurities concentrates REL 88
6.2. Study of the oxidation of impurities in REL concentrates 89
6.3. Semi-industrial tests on oxidative smelting and electrolysis of concentrates REL 97
6.4. Chapter 102 Conclusions
Conclusions on work 103
Literature 104
Introduction to work
The relevance of the work
Modern technology requires more and more noble metals. At present, the extraction of the latter has sharply decreased and does not meet the demand, therefore, it is necessary to use all the possibilities to mobilize the resources of these metals, and, consequently, the role of the secondary metallurgy of precious metals is increasing. In addition, the extraction of Au, Ag, Pt and Pd contained in waste is more profitable than from ores.
Changing the economic mechanism of the country, including military-industrial complex and the armed forces, necessitated the creation in certain regions of the country of complexes for the processing of scrap of the radio-electronic industry containing precious metals. At the same time, it is mandatory to maximize the extraction of precious metals from poor raw materials and reduce the mass of tailings-residues. It is also important that along with the extraction of precious metals, non-ferrous metals, such as copper, nickel, aluminum and others, can also be obtained.
The purpose of the work is the development of technology for the extraction of gold, silver, platinum, palladium and non-ferrous metals from scrap of the radio-electronic industry and technological waste from enterprises.
Basic provisions for defense
Pre-sorting REL with subsequent mechanical enrichment ensures the production of metal alloys with increased extraction of precious metals in them.
Physical and chemical analysis of parts of electronic scrap showed that the parts are based on up to 32 chemical elements, while the ratio of copper to the sum of the remaining elements is 50-r60: 50-0.
The low dissolution potential of copper-nickel anodes obtained by melting electronic scrap makes it possible to obtain
5 precious metal sludge suitable for processing according to standard technology.
Research methods. Laboratory, enlarged laboratory, industrial tests; analysis of the products of enrichment, melting, electrolysis was carried out chemical methods. For the study, the method of X-ray spectral microanalysis (XSMA) and X-ray phase analysis (XRF) was used using the DRON-06 setup.
Validity and reliability of scientific provisions, conclusions and recommendations due to the use of modern and reliable research methods and is confirmed by the good convergence of the results of complex studies performed in laboratory, enlarged laboratory and industrial conditions.
Scientific novelty
The main qualitative and quantitative characteristics of radio elements containing non-ferrous and precious metals are determined, which make it possible to predict the possibility of chemical and metallurgical processing of radio-electronic scrap.
The passivating effect of lead oxide films during the electrolysis of copper-nickel anodes made from electronic scrap has been established. The composition of the films is revealed and the technological conditions for the preparation of anodes are determined, which ensure the absence of a passivating effect condition.
The possibility of oxidation of iron, zinc, nickel, cobalt, lead, tin from copper-nickel anodes made from radio-electronic scrap was theoretically calculated and confirmed as a result of fire experiments at 75 "KIL0G P amm0B1Kh p Pbah melt, which ensures high technical and economic indicators of the recovery technology noble metals.
The practical significance of the work
A technological line for testing electronic scrap has been developed, including departments for disassembly, sorting, mechanical
smelting enrichment and analysis of noble and non-ferrous metals;
A technology has been developed for melting electronic scrap in induction
ion furnace, combined with the effect on the melt of oxidizing radial
but-axial jets, providing intensive mass and heat transfer in the zone
metal melting;
Developed and tested on a pilot scale technolo
graphical scheme for the processing of radio-electronic scrap and technological
of enterprises, providing individual processing and settlement with
by each REL supplier.
Approbation of work. The materials of the dissertation work were reported: on International Conference"Metallurgical technologies and equipment", April 2003, St. Petersburg; All-Russian scientific and practical conference"New technologies in metallurgy, chemistry, enrichment and ecology", October 2004, St. Petersburg; annual scientific conference of young scientists "Minerals of Russia and their development" March 9 - April 10, 2004, St. Petersburg; annual scientific conference of young scientists "Minerals of Russia and their development" March 13-29, 2006, St. Petersburg.
Publications. The main provisions of the dissertation were published in 7 printed works, including 3 patents for invention.
The materials of this work present the results of laboratory studies and industrial processing waste containing precious metals at the stages of disassembly, sorting and enrichment of radio-electronic scrap, smelting and electrolysis, carried out under industrial conditions of the SKIF-3 enterprise at the sites of the Russian Scientific Center "Applied Chemistry" and the Mechanical Plant named after. Karl Liebknecht.
Study of the material composition of electronic scrap
Currently, there is no domestic technology for the processing of poor electronic scrap. Purchasing a license from Western companies is impractical due to the dissimilarity of laws on precious metals. Western companies can buy radio-electronic scrap from suppliers, store and accumulate the amount of scrap up to a value that corresponds to the scale of the production line. The resulting precious metals are the property of the manufacturer.
In our country, according to the terms of cash settlements with scrap suppliers, each batch of waste from each deliverer, regardless of its size, must go through a full technological cycle of testing, including opening parcels, checking net and gross weights, averaging raw materials by composition (mechanical, pyrometallurgical, chemical) taking head samples , sampling from averaging by-products (slags, insoluble sediments, washing waters, etc.), encryption, analysis, interpretation of samples and certification of analysis results, calculation of the amount of precious metals in the batch, their acceptance on the balance sheet of the enterprise and registration of all accounting and settlement documentation.
After receiving semi-finished products concentrated in precious metals (for example, Doré metal), the concentrates are handed over to the state refinery, where, after refining, the metals go to the Gokhran, and payment for their value is sent back through the financial chain up to the supplier. It becomes obvious that for the successful operation of processing enterprises, each batch of the supplier must go through the entire technological cycle separately from the materials of other suppliers.
Analysis of the literature showed that one of possible ways The averaging of radio-electronic scrap is its firing at a temperature that ensures the combustion of the plastics that make up the REL, after which it is possible to melt the sinter, obtain an anode, followed by electrolysis.
Synthetic resins are used to make plastics. Synthetic resins, depending on the reaction of their formation, are divided into polymerized and condensed. There are also thermoplastic and thermosetting resins.
Thermoplastic resins can melt repeatedly upon reheating without losing their plastic properties, these include: polyvinyl acetate, polystyrene, polyvinyl chloride, condensation products of glycol with dibasic carboxylic acids, etc.
Thermosetting resins - when heated, they form infusible products, these include phenol-aldehyde and urea-formaldehyde resins, condensation products of glycerol with polybasic acids, etc.
Many plastics consist only of a polymer, these include: polyethylenes, polystyrenes, polyamide resins, etc. Most plastics (phenoplastics, aminoplastics, wood plastics, etc.) in addition to the polymer (binder) may contain: fillers, plasticizers, binders of curing and coloring agents, stabilizers and other additives. The following plastics are used in electrical engineering and electronics: 1. Phenoplasts - plastics based on phenolic resins. Phenoplasts include: a) cast phenolic plastics - hardened resins of the resol type, such as bakelite, carbolite, neoleukorite, etc.; b) layered phenolic plastics - for example, a pressed product made of fabric and resole resin, called textolite. Phenol-aldehyde resins are obtained by condensation of phenol, cresol, xylene, alkylphenol with formaldehyde, furfural. In the presence of basic catalysts, resole (thermosetting) resins are obtained, in the presence of acidic catalysts, novolac (thermoplastic resins) are obtained.
Technological calculations for the utilization of roasting gases
All plastics are mainly composed of carbon, hydrogen and oxygen with valence substitution by additives of chlorine, nitrogen, fluorine. Consider, as an example, the burning of textolite. Textolite is a flame-retardant material, it is one of the components of electronic scrap. It consists of pressed cotton fabric impregnated with artificial resole (formaldehyde) resins. Morphological composition of radio engineering textolite: - cotton fabric - 40-60% (average - 50%) - resole resin - 60-40% (average -50%) - (Cg H702) -m, where m is the coefficient corresponding to the products of the degree of polymerization. According to the literature data, when the ash content of the textolite is 8%, the humidity will be 5%. Chemical composition textolite in terms of the working mass will be,%: Cp-55.4; Hp-5.8; OP-24.0; Sp-0.l; Np-I.7; Fp-8.0; Wp-5, 0.
When burning 1 t/h of textolite, moisture evaporation is formed 0.05 t/h and ash 0.08 t/h. At the same time, it enters for combustion, t / h: C - 0.554; H - 0.058; 0-0.24; S-0.001, N-0.017. The composition of the ash textolite brand A, B, R according to the literature, %: CaO -40.0; Na, K20 - 23.0; Mg O - 14.0; RnO10 - 9.0; Si02 - 8.0; Al 203 - 3.0; Fe203 -2.7; SO3-0.3. For the experiments, firing was chosen in a sealed chamber without air access; for this, a box measuring 100x150x70 mm in size was made of stainless steel with a thickness of 3mm with a flange fastening of the lid. The lid to the box was fastened through an asbestos gasket with bolted joints. In the end surfaces of the box, choke holes were made through which the contents of the retort were purged with an inert gas (N2) and the gas products of the process were removed. The following samples were used as test samples: 1. Board cleaned from radio elements, sawn to the size of 20x20 mm. 2. Black circuit boards (full size 6x12 mm) 3. PCB connectors (sawed to 20x20 mm) 4. Thermosetting plastic connectors (sawed to 20x20 mm) The experiment was carried out as follows: 100 g of the test sample was loaded into the retort , was closed with a lid and placed in a muffle. The contents were purged with nitrogen for 10 minutes at a flow rate of 0.05 l/min. During the whole experiment, the nitrogen flow rate was maintained at the level of 20–30 cm3/min. Exhaust gases were neutralized with an alkaline solution. The muffle shaft was closed with brick and asbestos. The rise in temperature was regulated within 10-15C per minute. Upon reaching 600C, an hour exposure was carried out, after which the furnace was turned off and the retort was removed. During cooling, the nitrogen flow increased to 0.2 l/min. The results of the observation are presented in Table 3.2.
The main negative factor of the ongoing process is a very strong, sharp, unpleasant odor, which is emitted both from the cinder itself and from the equipment, which was "soaked" with this odor after the first experiment.
For the study, a continuous tubular rotary kiln with indirect electric heating was used with a batch capacity of 0.5-3.0 kg/h. The furnace consists of a metal casing (length 1040 mm, diameter 400 mm) lined with refractory bricks. The heaters are 6 silicate rods with a working part length of 600 mm, powered by two RNO-250 voltage variators. The reactor (total length 1560 mm) is a stainless steel tube with an outer diameter of 89 mm lined with porcelain pipe with an inner diameter of 73 mm. The reactor rests on 4 rollers and is equipped with a drive consisting of an electric motor, a gearbox and a belt drive.
To control the temperature in the reaction zone, a thermocouple, complete with a portable potentiometer, is installed inside the reactor. Preliminarily, its readings were corrected by direct measurements of the temperature inside the reactor.
Electronic scrap was manually loaded into the furnace at the ratio: boards cleaned of radio elements: black microcircuits: textolite connectors: thermoplastic resin connectors = 60:10:15:15.
This experiment was carried out on the assumption that the plastic would burn before it melted, which would ensure the release of the metal contacts. This turned out to be unattainable, as the pungent odor problem remains, and as soon as the connectors reached the temperature zone of -300C, the thermoplastic connectors adhered to the inner surface of the rotary kiln and blocked the passage of the entire mass of electronic scrap. Forced air supply to the furnace, temperature increase in the sticking zone did not lead to the possibility of firing.
Thermosetting plastic is also characterized by high viscosity and strength. A characteristic of these properties is that when cooled in liquid nitrogen for 15 minutes, the thermoset connectors were broken on an anvil using a ten-kilogram hammer without breaking the connectors. Given that the number of parts made from such plastics is small and they are well cut with a mechanical tool, it is advisable to disassemble them manually. For example, cutting or cutting connectors along the central axis leads to the release of metal contacts from the plastic base.
The range of electronic industry scrap entering for processing covers all parts and assemblies of various units and devices, in the manufacture of which precious metals are used.
The basis of the product containing precious metals, and, accordingly, their scrap, can be made of plastic, ceramics, fiberglass, multilayer material (BaTiOz) and metal.
Raw materials coming from delivering enterprises are sent for preliminary disassembly. At this stage, nodes containing precious metals are removed from electronic computers and other electronic equipment. They make up about 10-15% of the total mass of computers. Materials that do not contain precious metals are sent for the extraction of non-ferrous and ferrous metals. Waste material containing precious metals (printed circuit boards, plugs, wires, etc.) is sorted to remove gold and silver wires, gold-plated PCB side connector pins, and other parts with a high content of precious metals. The selected parts go directly to the precious metal refining section.
Testing the technology for obtaining concentrated gold and silver
A sample of a gold sponge weighing 10.10 g was dissolved in aqua regia, nitric acid was removed by evaporation with hydrochloric acid, and metallic gold was precipitated with a saturated solution of iron (II) sulfate prepared from carbonyl iron dissolved in sulfuric acid. The precipitate was repeatedly washed by boiling with distilled HCl (1:1) and water, and gold powder was dissolved in aqua regia prepared from acids distilled in a quartz vessel. The precipitation and washing operation was repeated and a sample was taken for emission analysis, which showed a gold content of 99.99%.
To carry out the material balance, the remains of the samples taken for analysis (1.39 g Au) and gold from the burned filters and electrodes (0.48 g) were combined and weighed, irretrievable losses amounted to 0.15 g, or 1.5% of the processed material . Such a high percentage of losses is explained by the small amount of gold involved in processing and the cost of the latter to fine-tune analytical operations.
Ingots of silver separated from the contacts were dissolved by heating in concentrated nitric acid, the solution was evaporated, cooled and drained from the precipitated salt crystals. The resulting precipitate of nitrate was washed with distilled nitric acid, dissolved in water and hydrochloric acid precipitated the metal in the form of chloride, the decanted mother liquor was used to develop the technology of refining silver by electrolysis.
The precipitate of silver chloride that settled during the day was washed with nitric acid and water, dissolved in an excess of aqueous ammonia, and filtered. The filtrate was treated with an excess of hydrochloric acid until the formation of sediment stops. The latter was washed with chilled water and metallic silver was isolated, which was pickled with boiling HCl, washed with water and melted with boric acid. The resulting ingot was washed with hot HCI (1:1), water, dissolved in hot nitric acid, and the whole cycle of silver extraction through chloride was repeated. After melting with flux and washing with hydrochloric acid, the ingot was remelted twice in a pyrographite crucible with intermediate operations to clean the surface with hot hydrochloric acid. After that, the ingot was rolled into a plate, its surface was etched with hot HCl (1:1), and a flat cathode was made for silver purification by electrolysis.
Metallic silver was dissolved in nitric acid, the acidity of the solution was adjusted to 1.3% with respect to HNO3, and this solution was electrolyzed with a silver cathode. The operation was repeated, and the resulting metal was fused in a pyrographite crucible into an ingot weighing 10.60 g. Analysis in three independent organizations showed that the mass fraction of silver in the ingot was at least 99.99%.
From a large number of works on the extraction of precious metals from semi-products, we chose for testing the method of electrolysis in a solution of copper sulphate.
62 g of metal contacts from the connectors were fused with borax and a flat ingot weighing 58.53 g was cast. The mass fraction of gold and silver is 3.25% and 3.1%, respectively. A portion of the ingot (52.42 g) was subjected to electrolysis as an anode in a solution of copper sulphate acidified with sulfuric acid, whereby 49.72 g of the anode material was dissolved. The resulting sludge was separated from the electrolyte, and after fractional dissolution in nitric acid and aqua regia, 1.50 g of gold and 1.52 g of silver were isolated. After burning the filters, 0.11 g of gold was obtained. The loss of this metal was 0.6%; irreversible loss of silver - 1.2%. The phenomenon of the appearance of palladium in solution (up to 120 mg/l) has been established.
During the electrolysis of copper anodes, the precious metals contained in it are concentrated in the sludge, which falls to the bottom of the electrolysis bath. However, a significant (up to 50%) transition of palladium into the electrolyte solution is observed. This work was carried out to cover the beginning of palladium losses.
The difficulty in extracting palladium from electrolytes is due to their complex composition. Works on sorption-extraction processing of solutions are known. The aim of the work is to obtain pure palladium mudflows and return the purified electrolyte to the process. To solve this problem, we used the process of metal sorption on synthetic ion-exchange fiber AMPAN H/SO4. Two solutions were used as initial solutions: No. 1 - containing (g/l): 0.755 palladium and 200 sulfuric acid; No. 2 - containing (g / l): palladium 0.4, copper 38.5, iron - 1.9 and 200 sulfuric acid. To prepare a sorption column, 1 gram of AMPAN fiber was weighed, placed in a column with a diameter of 10 mm, and the fiber was soaked for 24 hours in water.
Development of technology for the extraction of palladium from sulfuric acid solutions
The solution was supplied from below using a dosing pump. During the experiments, the volume of the passed solution was recorded. Samples taken at regular intervals were analyzed for palladium content by the atomic absorption method.
The results of the experiments showed that palladium adsorbed on the fiber is desorbed with a solution of sulfuric acid (200 g/l).
Based on the results obtained in the study of the processes of sorption-desorption of palladium on solution No. 1, an experiment was carried out to study the behavior of copper and iron in amounts close to their content in the electrolyte during sorption of palladium on the fiber. The experiments were carried out according to the scheme shown in Fig. 4.2 (Tables 4.1-4.3), which includes the process of sorption of palladium from solution No. 2 on the fiber, washing of palladium from copper and iron with a solution of 0.5 M sulfuric acid, desorption of palladium with a solution of 200 g / l sulfuric acid and washing the fiber with water (Fig. 4.3).
The products of enrichment obtained at the enrichment section of the SKIF-3 enterprise were taken as the feedstock for the melts. Melting was carried out in the "Tamman" furnace at a temperature of 1250-1450C in graphite-fireclay crucibles with a volume of 200 g (for copper). Table 5.1 presents the results of laboratory heats of various concentrates and their mixtures. Without complications, concentrates were melted, the compositions of which are presented in tables 3.14 and 3.16. Concentrates, the composition of which is presented in table 3.15, require a temperature in the range of 1400-1450C for melting. mixtures of these materials L-4 and L-8 require a temperature of the order of 1300-1350C for melting.
Industrial melts P-1, P-2, P-6, carried out in an induction furnace with a crucible with a volume of 75 kg for copper, confirmed the possibility of melting concentrates when the bulk composition of enriched concentrates was supplied to the melt.
In the process of research, it turned out that part of the electronic scrap is melted with large losses of platinum and palladium (concentrates from REL capacitors, Table 3.14). The loss mechanism was determined by adding silver and palladium surface-coated contacts to the surface of a copper molten bath (palladium content in contacts 8.0-8.5%). In this case, copper and silver melted out, leaving a palladium shell of contacts on the surface of the bath. An attempt to mix palladium into the bath led to the destruction of the shell. Part of the palladium flew off the surface of the crucible before it could dissolve in the copper bath. Therefore, all subsequent melts were carried out with cover synthetic slag (50% S1O2 + 50% soda).
Kozyrev, Vladimir Vasilievich
The invention relates to the metallurgy of noble metals and can be used in enterprises of secondary metallurgy for the processing of radio-electronic scrap and in the extraction of gold or silver from the waste of the electronic and electrochemical industry, in particular, to a method for extracting precious metals from the waste of the radio-electronic industry. The method includes obtaining copper-nickel anodes containing noble metal impurities from waste, their electrolytic anodic dissolution with copper deposition on the cathode, obtaining a nickel solution and sludge with noble metals. At the same time, anodic dissolution is carried out from an anode containing 6-10% iron, while placing the cathode and anode in separate mesh diaphragms to create cathode and anode spaces with a chlorine-containing electrolyte in them. The electrolyte obtained in the course of electrolysis is directed from the cathode space to the anode space. The technical result of the invention is a significant increase in the dissolution rate of the anode.
The invention relates to the metallurgy of precious metals and can be used in enterprises of secondary metallurgy for the processing of radio-electronic scrap and in the extraction of gold or silver from the waste of the electronic and electrochemical industries.
There are the following methods of electrorefining of metals.
There is a method that relates to the hydrometallurgy of precious metals, in particular to methods for extracting gold and silver from concentrates, waste from the electronic and jewelry industries. The method, in which the extraction of gold and silver includes treatment with solutions of complexing salts and the passage of an electric current with a density of 0.5-10 A / dm 2, solutions containing thiocyanate ions, ferric ions are used as solutions, and the pH of the solution is 0.5-4.0. The selection of gold and silver is carried out on the cathode, separated from the anode space by a filter membrane (RF Application No. 94005910, IPC C25C 1/20).
The disadvantages of this method are the increased loss of precious metals in the sludge. The method requires additional processing of concentrates with complexing salts.
An invention is known that relates to methods for extracting precious metals from spent catalysts, as well as to electrochemical processes with a fluidized or fixed bed. The processed material in the form of a backfill is placed in the interelectrode space of the electrolyzer, the electrochemical leaching of precious metals based on their anodic dissolution is activated by pre-treatment of the material by reversing the polarity of the electrodes in static, which turns it into a bulk multipolar electrode that provides anodic dissolution of the metal in the entire volume of the material, and electrolyte circulation through the backfill from the anode to the cathode, it is provided at a rate determined from the condition of preventing hydrated anionic chloride complexes of noble metals from entering the cathode, which are formed during leaching in the volume of the backfill, while acidified water with a hydrochloric acid content of 0.3-4.0 is used as an electrolyte %. The method allows to increase the productivity of the process and simplify it (RF Patent No. 2198947, IPC C25C 1/20).
The disadvantage of this method is the increased power consumption.
A known method includes the electrochemical dissolution of gold and silver in an aqueous solution at a temperature of 10-70°C in the presence of a complexing agent. Sodium ethylenediaminetetraacetate is used as a complexing agent. EDTA Na concentration 5-150 g/l. The dissolution is carried out at pH 7-14. Current density 0.2-10 A / dm 2. The use of the invention allows to increase the rate of dissolution of gold and silver; reduce the copper content in the sludge to 1.5-3.0% (RF Patent No. 2194801, IPC C25 C1 / 20).
The disadvantage of this method is not enough high dissolution rate.
As a prototype of the present invention, a method of electrolytic refining of copper and nickel from copper-nickel alloys containing impurities of precious metals is chosen, which includes electrochemical dissolution of anodes from a copper-nickel alloy, copper deposition to obtain a nickel solution and sludge. The dissolution of the anodes is carried out in an anode space separated by a diaphragm, in a suspended layer of sludge, while reducing power consumption (by 10%) and increasing the concentration of gold in the sludge. (Patent RF No. 2237750, IPC C25C 1/20, publ. 29.04.2003).
The disadvantages of this invention are the loss of precious metals in the sludge, insufficiently high dissolution rate.
The technical result is the elimination of these shortcomings, ie. reducing the loss of precious metals in the sludge, increasing the dissolution rate, reducing power consumption.
The technical result is achieved by the fact that in the method of electrolytic sulfuric acid dissolution of copper-nickel anodes obtained from radio-electronic industry waste containing impurities of noble metals, including anodic dissolution, chemical dissolution and cathodic copper deposition, to obtain a nickel solution and sludge with noble metals, according to the invention, the anode containing 6-10% iron and the cathode are placed in separate mesh diaphragms with a chlorine-containing electrolyte in them, and the electrolyte obtained in the process of electrolysis is sent from the cathode space to the anode space.
The method is implemented as follows.
In the electrolytic bath, the copper-nickel anode containing 6-10% iron, noble metal impurities, and the cathode are placed in separate mesh diaphragms with chlorine-containing electrolyte, creating separate anode and cathode spaces. In the cathode space, the electrolyte is enriched with ferric iron FeCl 3 and then it is fed into the anode space, for example, using a pump. The anode dissolution process is carried out at a current density of 2-10 A/dm 2 , a temperature of 40-70°C and a voltage of 1.5-2.5 V. metals in the sludge.
In the cathode space, an electrolyte enriched with FeCl 2 is formed, which is sent to the anode space, where it is oxidized to FeCl 3, due to which the process of chemical dissolution of the anode begins.
Due to the electrolytic and chemical action, the anode dissolution rate is significantly increased, the noble metal content in the sludge is increased, gold loss is reduced, and the anode dissolution time is shortened.
When the iron concentration in the anode is less than 6% in the electrolyte, a reduced content of FeCl 3 is observed, which leads to insufficient chemical action of ferric iron FeCl 3 on the anode and, as a result, a low rate of dissolution of the anode.
An increase in the iron concentration in the anode above 10% does not contribute to a further increase in the rate of dissolution of the anode, but creates additional difficulties in the processing of the electrolyte.
This method is proved by the following examples.
A copper-nickel anode containing 7% Fe and weighing 119 g was placed in the anode space and dissolved at a voltage of 2.5 V, a temperature of 60°C and a current density of 1000 A/m 2 in an electrolyte of the following composition: CuSO 4 5H 2 O - 500 ml, H 2 SO 4 - 250 ml, FeSO 4 - 60 ml, HCl - 50 ml. In the absence of electrolyte circulation, the mass of the anode during the first hour of the process decreased by 0.9 g. During two hours of electrolysis, the mass of the anode decreased by 1.8 g.
After the electrolyte began to be moved from the cathode space to the anode space without changing the current density, the mass of the anode decreased by 4.25 g in the first hour of electrolysis, and by 8.5 g in two hours.
A copper-nickel anode containing 4% Fe and weighing 123 g was dissolved under the same conditions, and in the absence of electrolyte circulation, the mass of the anode during the first hour of the process decreased by 0.4 g, and after two hours of electrolysis, the mass of the anode decreased by 0.8 G.
Moving the electrolyte from the cathode space to the anode space without changing the current density made it possible to reduce the mass of this anode by 1.15 g in the first hour of electrolysis, and by 2.3 g in two hours.
Under the condition of moving the electrolyte from the cathode space to the anode space, the mass of the anode decreased by 4.25 g in the first hour of electrolysis, and by 8.5 g in two hours.
Based on the data obtained, it can be concluded that the iron content of 6-10% in the copper-nickel anode and the movement of the electrolyte enriched with FeCl 3 from the cathode space to the anode space can significantly increase the anode dissolution rate.
Thanks to the proposed method, the following effects are achieved:
1) increase in the content of precious metals in the sludge;
2) a significant increase in the rate of dissolution of the anode;
3) reduction of sludge volume.
CLAIM
A method for extracting noble metals from wastes of the electronic industry, including obtaining copper-nickel anodes from them containing impurities of noble metals, their electrolytic anodic dissolution with copper deposition on the cathode and obtaining a nickel solution and sludge with noble metals, characterized in that electrolytic anodic dissolution is carried out an anode containing 6-10% iron, when the cathode and anode are placed in separate mesh diaphragms to create cathode and anode spaces with a chlorine-containing electrolyte in them, and the electrolyte obtained in the electrolysis process is sent from the cathode space to the anode space.
The technology being developed at the Ginalmazzoloto Research Institute is focused on obtaining mainly noble metals from elements and components of electronic scrap containing them. Another feature of the technology is the widespread use of separation methods in liquid media and some other methods typical for the enrichment of non-ferrous metal ores.
VNIIPvtortsvetmet specializes in processing technologies for certain types of scrap: printed circuit boards, electronic vacuum devices, PTK blocks in TVs, etc.
By density, the board material is divided with a high degree of reliability into two fractions: a mixture of metals and non-metals (+1.25 mm) and non-metals (-1.25 mm). Such a separation can be carried out on a screen. In turn, a metal fraction can be separated from the non-metal fraction during additional separation on a gravitational separator, and thereby a high degree of concentration of the resulting materials is achieved.
Part (80.26%) of the remaining material +1.25 mm can be subjected to repeated crushing to a fineness of -1.25 mm, followed by separation of metals and non-metals from it.
At the TEKON plant in St. Petersburg, a production complex for extracting precious metals has been installed and is being operated. Using the principles of shock-speed crushing of the original scrap (products for microwave technology, reading devices, microelectronic circuits, printed circuits, Pd-catalysts, printed circuit boards, electroplating waste) on installations (rotor-knife shredder, high-speed rotary impact disintegrator, drum screen, electrostatic separator, magnetic separator) selectively disintegrated material is obtained, which is further separated by magnetic and electrical separation methods into fractions represented by non-metals, ferrous metals and non-ferrous metals enriched in platinoids, gold and silver. Further, precious metals are separated by refining.
This method is designed to obtain a polymetallic concentrate containing silver, gold, platinum, palladium, copper, and other metals, with a non-metallic fraction content of not more than 10%. The technological process allows for the extraction of metal, depending on the quality of the scrap, by 92-98%.
Waste of electrical and radio engineering production, mainly boards, usually consists of two parts: mounting elements (microcircuits) containing precious metals and a base that does not contain precious metals with an incoming part glued to it in the form of copper foil conductors. Therefore, according to the method developed by the Mekhanobr-Tekhnogen association, each of the components is subjected to a softening operation, as a result of which the laminate loses its original strength characteristics. Softening is carried out in a narrow temperature range of 200-210ºС for 8-10 hours, then dried. Below 200ºС, softening does not occur, above the material "floats". During subsequent mechanical crushing, the material is a mixture of laminate grains with disintegrated mounting elements, a conductive part and caps. The softening operation in aquatic environment prevents harmful secretions.
Each size class of the material classified after crushing (-5.0 + 2.0; -2.0 + 0.5 and -0.5 + 0 mm) is subjected to electrostatic separation in the corona discharge field, resulting in the formation of fractions: metal elements of the boards and non-conductive - a fraction of laminated plastic of the appropriate size. Then solder and concentrates of precious metals are obtained from the metal fraction. The non-conductive fraction after processing is used either as a filler and pigment in the production of varnishes, paints, enamels, or again in the production of plastics. Thus, the essential distinguishing features are: softening of electrical waste (boards) before crushing in an aqueous medium at a temperature of 200-210ºС, and classification into certain fractions, each of which is then processed with further use in industry.
The technology is characterized by high efficiency: the conductive fraction contains 98.9% of the metal with its extraction of 95.02%; the non-conductive fraction contains 99.3% of the modified fiberglass with its extraction of 99.85%.
There is another way to extract precious metals (patent of the Russian Federation RU2276196). It includes the disintegration of electronic scrap, vibration treatment with separation of the heavy fraction containing precious metals, separation and separation of metals. At the same time, the obtained electronic scrap is sorted and metal parts are separated, the remaining part of the scrap is subjected to vibration treatment with separation of the heavy fraction and separation. After separation, the heavy fraction is mixed with pre-separated metal parts and the mixture is subjected to oxidative melting when air blast is supplied in the range of 0.15-0.25 nm3 per 1 kg of the mixture, after which the resulting alloy is electrorefined in a copper sulfate solution and precious metals are isolated from the formed sludge. metals. The method provides a high recovery of precious metals, %: gold - 98.2; silver - 96.9; palladium - 98.2; platinum - 98.5.
Directly, there are practically no programs for the systematic collection and disposal of used electronic and electrical equipment in Russia.
In 2007, on the territory of Moscow and the Moscow region, in accordance with the order of the Moscow government "On the creation of an urban system for the collection, processing and disposal of electronic and electrical waste", they were going to select land for development production capacity Ecocenter of Moscow State Unitary Enterprise "Promothody" for the collection and industrial processing of waste with the allocation of zones for the disposal of scrap electronic and electrical products within the areas planned for sanitary cleaning facilities.
As of October 30, 2008, the project had not yet been implemented, and in order to optimize the expenditures of the Moscow city budget for 2009-2010 and the planned period of 2011-2012, Moscow Mayor Yuri Luzhkov, in difficult financial and economic conditions, ordered to suspend earlier decisions made on the construction and operation of a number of waste processing enterprises and factories in Moscow.
Orders suspended include:
- "On the procedure for attracting investments to complete the construction and operation of a waste transfer complex in the Yuzhnoye Butovo industrial zone of the city of Moscow";
- "On organizational support for the construction and operation of a waste processing plant at the address: Ostapovsky proezd, 6 and 6a (South-Eastern administrative district of Moscow)";
- "On the introduction of an automated system for monitoring the turnover of production and consumption waste in the city of Moscow";
- "On the design of a complex enterprise for sanitary cleaning of the State Unitary Enterprise "Ecotechprom" at the address: Vostryakovsky proezd, vl.10 (Southern Administrative District of Moscow)".
The deadlines for the implementation of the orders have been postponed to 2011:
- Order No. 2553-RP "On organizing the construction of a production and storage technological complex with elements for sorting and preliminary processing of bulky waste in the Kuryanovo industrial zone";
- Order No. 2693-RP "On the creation of a waste processing complex".
The decree “On the creation of a city system for the collection, processing and disposal of electronic and electrical waste” was also recognized as invalid.
A similar situation is observed in many cities of the Russian Federation, and at the same time it is aggravated during the economic crisis.
Now in Russia there is a law that regulates the handling of consumer waste, which includes used household appliances, for violation of which a fine is provided: for citizens - 4-5 thousand rubles; for officials - 30-50 thousand rubles; for legal entities- 300-500 thousand rubles. But at the same time, throwing an old refrigerator, radio, or any part of the car into the trash is still the easiest way to get rid of old equipment. Moreover, you can be fined only if you decide to leave the trash just on the street, in a place not intended for this.
M.Sh. BARKAN, Ph.D. tech. Sciences, Associate Professor, Department of Geoecology, [email protected]
M.I. CHINENKOVA, undergraduate, Department of Geoecology
St. Petersburg State Mining University
LITERATURE
1. Secondary silver metallurgy. Moscow State Institute of Steel and Alloys. - Moscow. – 2007.
2. Getmanov V.V., Kablukov V.I. Electrolytic waste recycling
means of computer technology containing precious metals // MSTU " Ecological problems modernity". – 2009.
3. Patent of the Russian Federation RU 2014135
4. Patent of the Russian Federation RU2276196
5. Complex of equipment for processing and sorting of electronic and electrical scrap and cable. [Electronic resource]
6. Utilization of office equipment, electronics, household appliances. [Electronic resource]
Chapter 1. LITERATURE REVIEW.
Chapter 2. STUDY OF THE MATTER COMPOSITION
RADIO-ELECTRONIC SCRAP.
Chapter 3. DEVELOPMENT OF AVERAGING TECHNOLOGY
RADIO-ELECTRONIC SCRAP.
3.1. Roasting of electronic scrap.
3.1.1. Information about plastics.
3.1.2. Technological calculations for the utilization of roasting gases.
3.1.3. Roasting electronic scrap in the lack of air.
3.1.4. Roasting electronic scrap in a tube furnace.
3.2 Physical methods of processing electronic scrap.
3.2.1. Description of the enrichment area.
3.2.2. Technological scheme of the enrichment section.
3.2.3. Development of enrichment technology at industrial units.
3.2.4. Determination of the productivity of the units of the enrichment section during the processing of electronic scrap.
3.3. Industrial testing of enrichment of electronic scrap.
3.4. Conclusions to chapter 3.
Chapter 4. DEVELOPMENT OF TECHNOLOGY FOR PROCESSING RADIO-ELECTRONIC SCRAP CONCENTRATES.
4.1. Research on the processing of REL concentrates in acid solutions.
4.2. Testing the technology for obtaining concentrated gold and silver.
4.2.1. Testing the technology for obtaining concentrated gold.
4.2.2. Testing the technology for obtaining concentrated silver.
4.3. Laboratory research on the extraction of gold and silver REL by melting and electrolysis.
4.4. Development of technology for the extraction of palladium from sulfuric acid solutions.
4.5. Conclusions to chapter 4.
Chapter 5
5.1. Smelting of metal concentrates REL.
5.2. Electrolysis of REL smelting products.
5.3. Conclusions to chapter 5.
Chapter 6
6.1. Thermodynamic calculations of the oxidation of REL impurities.
6.2. Study of the oxidation of impurities in REL concentrates.
6.3. Semi-industrial tests on oxidative melting and electrolysis of REL concentrates.
6.4. Chapter conclusions.
Recommended list of dissertations
Processing technology for polymetallic raw materials containing platinum and palladium 2012, candidate of technical sciences Rubis, Stanislav Aleksandrovich
Development of technology for dissolving copper-nickel anodes containing precious metals at high current densities 2009, candidate of technical sciences Gorlenkov, Denis Viktorovich
Research, development and implementation of technologies for processing nickel and copper man-made waste to obtain finished metal products 2004, Doctor of Technical Sciences Zadiranov, Alexander Nikitovich
Scientific substantiation and development of technology for the complex processing of copper electrolyte sludge 2014, Doctor of Technical Sciences Sergey Mastyugin
Development of environmentally friendly technologies for the integrated extraction of precious and non-ferrous metals from electronic scrap 2010, Doctor of Technical Sciences Loleit, Sergey Ibragimovich
Introduction to the thesis (part of the abstract) on the topic "Development of an effective technology for the extraction of non-ferrous and noble metals from the waste of the radio engineering industry"
The relevance of the work
Modern technology requires more and more noble metals. At present, the extraction of the latter has sharply decreased and does not meet the demand, therefore, it is necessary to use all the possibilities to mobilize the resources of these metals, and, consequently, the role of the secondary metallurgy of precious metals is increasing. In addition, the extraction of Au, Ag, Pt and Pd contained in waste is more profitable than from ores.
The change in the economic mechanism of the country, including the military-industrial complex and the armed forces, necessitated the creation in certain regions of the country of complexes for the processing of scrap from the radio-electronic industry containing precious metals. At the same time, it is mandatory to maximize the extraction of precious metals from poor raw materials and reduce the mass of tailings-residues. It is also important that along with the extraction of precious metals, non-ferrous metals, such as copper, nickel, aluminum and others, can also be obtained.
The aim of the work is to develop a technology for the extraction of gold, silver, platinum, palladium and non-ferrous metals from scrap of the radio-electronic industry and technological waste from enterprises.
Basic provisions for defense
1. Pre-sorting of REL with subsequent mechanical enrichment ensures the production of metal alloys with an increased extraction of precious metals in them.
2. Physical and chemical analysis of parts of electronic scrap showed that the parts are based on up to 32 chemical elements, while the ratio of copper to the sum of the remaining elements is 50-g60: 50-100.
3. The low dissolution potential of copper-nickel anodes obtained by smelting radio-electronic scrap makes it possible to obtain precious metal sludge suitable for processing using standard technology.
Research methods. Laboratory, enlarged laboratory, industrial tests; analysis of products of enrichment, melting, electrolysis was carried out by chemical methods. For the study, the method of X-ray spectral microanalysis (XSMA) and X-ray phase analysis (XRF) was used using the DRON-Ob installation.
The validity and reliability of scientific provisions, conclusions and recommendations are due to the use of modern and reliable research methods and is confirmed by the good convergence of the results of complex studies performed in laboratory, enlarged laboratory and industrial conditions.
Scientific novelty
The main qualitative and quantitative characteristics of radio elements containing non-ferrous and precious metals are determined, which make it possible to predict the possibility of chemical and metallurgical processing of radio-electronic scrap.
The passivating effect of lead oxide films during the electrolysis of copper-nickel anodes made from electronic scrap has been established. The composition of the films is revealed and the technological conditions for the preparation of anodes are determined, which ensure the absence of a passivating effect condition.
The possibility of oxidation of iron, zinc, nickel, cobalt, lead, tin from copper-nickel anodes made from electronic scrap was theoretically calculated and confirmed as a result of fire experiments on 75-kilogram melt samples, which ensures high technical and economic indicators of the noble metal recovery technology.
The practical significance of the work
A technological line for testing radio-electronic scrap has been developed, including departments for disassembly, sorting, mechanical enrichment of melting and analysis of precious and non-ferrous metals;
A technology has been developed for melting radio-electronic scrap in an induction furnace, combined with the effect of oxidizing radial-axial jets on the melt, providing intensive mass and heat transfer in the metal melting zone;
A technological scheme for the processing of radio-electronic scrap and technological waste from enterprises has been developed and tested on a pilot industrial scale, which ensures individual processing and settlement with each REL supplier.
Approbation of work. The materials of the dissertation work were reported: at the International Conference "Metallurgical technologies and equipment", April 2003, St. Petersburg; All-Russian scientific and practical conference "New technologies in metallurgy, chemistry, enrichment and ecology", October 2004, St. Petersburg; annual scientific conference of young scientists "Minerals of Russia and their development" March 9 - April 10, 2004, St. Petersburg; annual scientific conference of young scientists "Minerals of Russia and their development" March 13-29, 2006, St. Petersburg.
Publications. The main provisions of the dissertation were published in 7 printed works, including 3 patents for invention.
The materials of this work present the results of laboratory studies and industrial processing of waste containing precious metals at the stages of disassembly, sorting and enrichment of radio-electronic scrap, smelting and electrolysis, carried out under industrial conditions at the SKIF-3 enterprise at the sites of the Russian Scientific Center "Applied Chemistry" and a mechanical plant them. Karl Liebknecht.
Similar theses in the specialty "Metallurgy of ferrous, non-ferrous and rare metals", 05.16.02 VAK code
Research and development of technology for obtaining silver from silver-zinc batteries containing lead by two-stage oxidative melting 2015, candidate of technical sciences Rogov, Sergey Ivanovich
Research and development of technology for chlorination leaching of platinum and palladium from secondary raw materials 2003, candidate of technical sciences Zhiryakov, Andrey Stepanovich
Development of a technology for the extraction of non-precious elements from the original concentrates and middlings of refining production 2013, candidate of technical sciences Mironkina, Natalia Viktorovna
Development of technology for briquetting sulfide high-magnesium copper-nickel raw materials 2012, Ph.D. Mashyanov, Alexey Konstantinovich
Reducing losses of platinum group metals during pyrometallurgical processing of copper and nickel sludge 2009, Candidate of Technical Sciences Pavlyuk, Dmitry Anatolyevich
Dissertation conclusion on the topic "Metallurgy of ferrous, non-ferrous and rare metals", Telyakov, Alexey Nailievich
CONCLUSIONS ON THE WORK
1. Based on the analysis of literary sources and experiments, a promising method for processing electronic scrap has been identified, including sorting, mechanical enrichment, smelting and electrolysis of copper-nickel anodes.
2. A technology for testing radio-electronic scrap has been developed, which makes it possible to process separately each technological batch of the supplier with the quantitative determination of metals.
3. Based on comparative tests of 3 head crushers (cone inertial crusher, jaw crusher, hammer crusher), a hammer crusher is recommended for industrial implementation.
4. On the basis of the research carried out, a pilot plant for the processing of electronic scrap was manufactured and put into production.
5. In laboratory and industrial experiments, the effect of "passivation" of the anode was studied. The existence of a sharply extreme dependence of the lead content in a copper-nickel anode made from electronic scrap has been established, which should be taken into account when controlling the process of oxidative radial-axial melting.
6. As a result of semi-industrial testing of the technology for processing radio-electronic scrap, initial data for the construction of a plant for processing waste from the radio engineering industry have been developed.
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