Technology for extracting precious metals from electrical waste. The method of processing electrical and radio engineering waste Approximate word search

Use: Economically pure recycling of waste electrical and radio engineering production with the maximum degree of discharge of components. SUMMARY OF THE INVENTION: Waste first decorate in an autoclave in an aqueous medium at a temperature of 200 - 210 ° C for 8 - 10 hours, then dried, crushed and classified according to fractions - 5.0 + 2.0; -2.0 + 0.5 and -0.5 + 0 mm, followed by electrostatic separation. 5 table.

The invention relates to electrical engineering, in particular to the disposal of printed circuit boards, and can be used to extract precious metals with subsequent use, as well as in the chemical industry in the production of dyes. There is a method of processing electrical waste - boards with the basis of ceramics (Avt. St. 1368029, cl. In 02 C, 1986), which consists in two-stage crushing without discraining abrasive components in order to delay the metal component. The boards are pulled in a small amount to nickel ore raw materials and the mixture is mowed in ore-thermal furnaces at a temperature of 1350 o C. The described method has a number of significant flaws: low efficiency; Danger from the point of view of ecology - high content of layered plastic and insulating materials when melting leads to infection ambient ; Losses are chemically associated with volatile noble metals. There is a method of disposal of secondary raw materials (N. Beliell et al. 89), adopted for the prototype. This method is characterized by hydrometallurgical recycling of boards - by treatment with nitric acid or a solution of copper nitrate in nitric acid. The main disadvantages: environmental pollution, the need to organize wastewater treatment; The problem of the electrolysis of the solution, which makes it almost impossible to specified technology non-frequency. The closest in technical essence is the method of processing electronic equipment scrap (Scrap Processor Awaits Refinery. Metall Bulletin Monthly, March, 1986, R. 19), adopted for a prototype, which includes crushing with subsequent separation. The separator is equipped with a magnetic drum, a cryogenic mill and sieves. The main disadvantage of the method - during separation, the structure of the components is changing. In addition, the method provides only primary processing of raw materials. This invention is directed to the implementation of environmentally friendly non-waste technology. The invention differs from the prototype in that in the method of processing electrical waste, including crushing of material, followed by classification by size, waste before crushing is subjected to decomposition in the autoclave in an aqueous medium at a temperature of 200-210 o C for 8-10 hours, then dried, classification are carried out according to fractions -5.0 + 2.0; -2.0 + 0.5 and -0.5 + 0 mm, and separation is electrostatic. The essence of the invention is as follows. Waste electrical and radiotechnical production, mainly fees, consist, as a rule, of two parts: installation elements (chip) containing precious metals and non-containing basic precious metals with an incoming part in the form of copper foil conductors. Each component is subjected to dispersion operation, as a result of which the layered plastic loses its initial strength characteristics. The softening is produced in a narrow temperature range 200-210 o C, below 200 o with softening does not occur, above the material "floats". With a subsequent mechanical crushing, the crushed material is a mixture of grains of layered plastic with disintegrated installation elements conducted by part and pistons. Operarination operation in the aquatic environment prevents harmful allocations. Each class of the size of the exposed after crushing of the material is subjected to electrostatic separation in the field of the corona discharge, as a result of which fractions are formed: conducting all metallic elements of boards and non-conductive - fraction of layered plastic of appropriate size. Then the known methods made of metal fractions are obtained by solder and slices of precious metals. The non-conductive fraction after treatment is used either as a filler and pigment in the production of varnishes, paints, enamels, or re-in the production of plastics. Thus, the substantial distinctive features are: the softening of electrical waste (boards) before crushing in aqueous medium at a temperature of 200-210 o C, and the classification according to certain fractions, each of which is then processed with further use in industry. The stated method was tested in the laboratory of the Institute "Mehanob". The processing was subjected to a marriage formed during the production of boards. The basis of waste - sheet glass fiberstitol in epoxytoplast with a thickness of 2.0 mm with the presence of contact copper conductors from foil coated with the solder and fifth. Operarification of boards were produced in an autoclave of 2l. At the end of the experience, the autoclave left 20 o C, then the material was unloaded, subjected to drying, and then crushing, first in the hammer crusher, and then in the cone - inertial crusher KID-300. The processing mode and its results are presented in Table. 1. The particle size characteristic of crushed material experience in optimal mode after drying is presented in Table. 2. The subsequent electrostatic separation of these classes was produced in the field of the corona discharge carried out on the drum electrostatic separator SB-32/50. From these tables follows / that the proposed technology is characterized by high efficiency: the conductive fraction contains 98.9% of the metal when it is removed by 95.02%; The non-conductive fraction contains 99.3% of the modified glasskeepolite when it is removed by 99.85%. Similar results were obtained and when processing waste boards with elements of mounting in the form of chips. The basis of the board is a fiberglass in epoxycoplast. In these studies, the optimal regime of softening, crushing and electrostatic separation was also used. The board using a mechanical cutter was previously separated into two components: containing and not containing precious metals. In the component with precious metals, along with a fiberglass, copper foil, ceramics and soldiers, attended palladium, gold and silver. The remaining part of the board is shown by the cutter is represented by copper foil contacts, shifting and pistons located in accordance with the radio engineering scheme on a fiberglass reservoir in epoxy resin. Thus, the processing was subjected to both components of the boards. Research results are placed in Table. 5, the data of which confirms the high efficiency of the claimed technology. Thus, in a conductive fraction containing 97.2% of the metal, it has been reached with 97.73%; In a non-conductive fraction containing 99.5% modified fiberglass, the extraction of the latter was 99.59%. Thus, the use of the claimed method will allow to obtain the technology for the processing of electrical, radiotechnical waste is practically waste-free and environmentally friendly. The conductive fraction (metal) is subject to processing into commercial metals by known methods of pyro- and (or) hydrometallurgy, including electrolysis: concentrate (slots) of precious metals, copper foil, tin and lead. The non-conductive fraction is a modified fiberglass in epoxidoplast - it is easily ground to a powder suitable as a pigment in paint production in the manufacture of varnishes, paints and enamels.

Chapter 1. Review of literature.

Chapter 2. Study of the real composition

Radioelectronic scrap.

Chapter 3. Development of averaging technology

Radioelectronic scrap.

3.1. Firing radio electronic scrap.

3.1.1. Plastic information.

3.1.2. Technological calculations of the disposal of oblique gases.

3.1.3. Firing of radio electronic scrap in air deficiency.

3.1.4. Firing of radio-electronic scrap in a tubular furnace.

3.2 Physical methods for processing radio-electronic scrap.

3.2.1. Description of the processing plot.

3.2.2. Technological scheme of the enrichment site.

3.2.3. The development of enrichment technology on industrial units.

3.2.4. Determination of the productivity of the aggregates of the enrichment section in the processing of radio-electronic scrap.

3.3. Industrial trials of enrichment of radio electronic scrap.

3.4. Conclusions to the 3 chapter.

Chapter 4. Development of technology for processing concentrates of radio-electronic scrap.

4.1. Research for the processing of RAL concentrates in acid solutions.

4.2. Turning the technology of obtaining concentrated gold and silver.

4.2.1. Testing the technology of obtaining concentrated gold.

4.2.2. Testing the technology of obtaining concentrated silver.

4.3. Laboratory studies on the extraction of gold and silver REL fuscoach and electrolysis.

4.4. Development of palladium extraction technology from sulfuric acid solutions.

4.5. Conclusions to chapter 4.

Chapter 5. Semi-industrial melting tests and electrolysis of concentrates of radio-electronic scrap.

5.1. Melting Metal Concentrate Ral.

5.2. Electrolysis Melting products RAL.

5.3. Conclusions to 5 chapter.

Chapter 6. Studying the oxidation of impurities when smelting radio-electronic scrap.

6.1. Thermodynamic calculations of the oxidation of RAL impurities.

6.2. Study of the oxidation of impurities of RAL concentrates.

6.3. Semi-industrial tests for oxidative welding and electrolysis of RAL concentrates.

6.4. Conclusions on the chapter.

Recommended list of dissertations

• Technology of processing of polymetallic raw materials containing platinum and palladium 2012, candidate of technical sciences Rubbish, Stanislav Aleksandrovich

• Development of the technology of dissolving copper-nickel anodes containing precious metals, at high current densities 2009, Candidate of Technical Sciences Gorlenkov, Denis Viktorovich

• Research, development and implementation of non-nickel and copper technologies for the processing technologies to obtain finished metal products 2004, Doctor of Technical Sciences Zadiyanov, Alexander Nikitovich

• Scientific substantiation and development of the technology of complex processing of medeloelectrolytic sludge 2014, Doctor of Technical Sciences Mastyugin, Sergey Arkadyevich

• Development of environmentally friendly technologies for complex extraction of noble and non-ferrous metals from electronic scrap 2010, Doctor of Technical Sciences Loleit, Sergey Ibrahimovich

The dissertation (part of the author's abstract) on the topic "Development of an effective technology for extracting non-ferrous and noble metals from the waste radiotechnical industry"

Similar dissertation work in the specialty "Metallurgy of black, non-ferrous and rare metals", 05.16.02 CIFRA WAK

• Research and development of silver technology from silver-zinc batteries containing lead, two-stage oxidative melting 2015, Candidate of Technical Sciences Rogov, Sergey Ivanovich

• Research and development of the technology of chlorinational leaching platinum and palladium from secondary raw materials 2003, Candidate of Technical Sciences Zhenakov, Andrey Stepanovich

• Development of technology for extracting non-procurement elements from the initial concentrates and industrial industrial production industries 2013, Candidate of Technical Sciences Mironkin, Natalia Viktorovna

• Development of briquetting technology sulfide high-challenging copper-nickel raw materials 2012, Candidate of Technical Sciences Mashyanov, Alexey Konstantinovich

• Reducing the loss of metal platinum groups during pyrometallurgical processing of copper and nickel sludge 2009, Candidate of Technical Sciences Pavlyuk, Dmitry Anatolyevich

Conclusion of dissertation on the topic "Metallurgy of black, non-ferrous and rare metals", calves, Alexey Nailievich

References dissertation research candidate of Technical Sciences Telyakov, Alexey Nailievich, 2007

Note the above scientific texts Posted for familiarization and obtained by recognizing original texts of theses (OCR). In this connection, they may contain errors associated with the imperfection of recognition algorithms. In PDF the dissertation and the author's abstracts that we deliver such errors.

480 rub. | 150 UAH. | $ 7.5 ", Mouseoff, Fgcolor," #FFFFCC ", BGColor," # 393939 ");" Onmouseout \u003d "Return nd ();"\u003e Dissertation period - 480 rub., Delivery 10 minutes , around the clock, seven days a week and holidays

Veliakov Alexey Nail'evich. Development of effective technology for extracting non-ferrous and noble metals from waste of radio engineering industries: the dissertation ... Candidate of Technical Sciences: 05.16.02 St. Petersburg, 2007 177 p., Bibliogr.: With. 104-112 RGB OD, 61: 07-5 / 4493

Introduction

Chapter 1. Review of Literature 7

Chapter 2. Study of the real composition of the radio electronic scrap 18

Chapter 3. Development of technology averaging radio electronic scrap 27

3.1. Firing Radio Electronic Scrap 27

3.1.1. Plastic Information 27

3.1.2. Technological calculations of the disposal of oblique gases 29

3.1.3. Firing of radio electronic scrap in air deficiency 32

3.1.4. Firing of radio electronic scrap in a tubular furnace 34

3.2 Physical methods for processing radio-electronic scrap 35

3.2.1. Description of the processing plot 36

3.2.2. Technological scheme of the enrichment area 42

3.2.3. Development of enrichment technology on industrial aggregates 43

3.2.4. Determination of the productivity of the aggregates of the enrichment section in the processing of radio-electronic scrap 50

3.3. Industrial trials of enrichment of radio electronic scrap 54

3.4. Conclusions to 3 chapter 65

Chapter 4. Development of technology for processing concentrates of radio-electronic scrap . 67

4.1. Research for the processing of RAL concentrates in solutions of acids .. 67

4.2. Testing the technology of obtaining concentrated gold and silver 68

4.2.1. Turning the technology of obtaining concentrated gold 68

4.2.2. Turning the technology of obtaining concentrated silver ... 68

4.3. Laboratory research on the extraction of gold and silver RAL fusible and electrolysis 69

4.4. Development of palladium extraction technology from sulfuric acid solutions. 70.

4.5. Conclusions to chapter 4 74

Chapter 5. Semi-industrial melting and electrolysis of radio electronic scrap concentrates 75

5.1. Melting Metal Cointers RAL 75

5.2. Electrolysis Melting products RAL 76

5.3. Conclusions to 5 chapter 81

Chapter 6. Studying the oxidation of impurities when weaving radio-electronic scrap 83

6.1. Thermodynamic calculations of the oxidation of the impurities RAL 83

6.2. Study of the oxidation of impurities of RAL 88 concentrates

6.2. Study of the oxidation of impurities of RAL 89 concentrates

6.3. Semi-industrial tests for oxidative melting and electrolysis of RAL 97 concentrates

6.4. Conclusions on chapter 102

Conclusions for work 103

Literature 104.

Introduction to work

Relevance of work

Modern technology needs increasing amounts of noble metals. Currently, the prey of the latter declined sharply and does not provide needs, so it is necessary to use all the possibilities for mobilizing the resources of these metals, and, therefore, the role of secondary metallurgy of noble metals is increasing. In addition, the extraction of AU, AG, PT and PDs contained in waste is more profitable than from ores.

Changing the economic mechanism of the country, including the military-industrial complex and armed forces, led to the need to create in certain regions of the country's processing complexes for the scrap of electronic industries containing precious metals. In this case, the maximum extraction of precious metals from poor raw materials and a decrease in the mass of residual tailings is obligatory. It is also important that along with the extraction of precious metals, non-ferrous metals can be obtained, for example, copper, nickel, aluminum and others.

Goal goalit is the development of gold, silver, platinum, palladium, silver, platinum, palladium and non-ferrous metals from the leoms of the radio electronic industry and technological waste of enterprises.

The main provisions endowed

Pre-sorting of REL followed by mechanical enrichment provides metal alloys with increased extraction in them precious metals.

The physico-chemical analysis of the details of the radio 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-yo.

The low potential for the dissolution of copper-nickel anodes obtained during smelting of radio-electronic scrap provides the possibility of obtaining

5 shelves of noble metals suitable for processing according to standard technology.

Research methods.Laboratory, enlarge-laboratory, industrial tests; Analysis of enrichment products, smelting, electrolysis was carried out by chemical methods. For the study, the X-ray microanalysis method (RSMA) and X-ray phase analysis (RFA) was used using the DRON-06 installation.

Rationalth and accuracy of scientific provisions, conclusions and recommendationsdefended by using modern and reliable research methods and is confirmed by the good convergence of the results of comprehensive research performed in laboratory, enlargeous-laboratory and industrial conditions.

Scientific novelty

The main qualitative and quantitative characteristics of radiole elements containing non-ferrous and precious metals are determined to predict the possibility of chemical and metallurgical processing of radio-electronic scrap.

The passivating effect of lead oxide films under electrolysis of copper-nickel anodes made from electronic scrap is established. The composition of the films was revealed and technological conditions for the preparation of the anodes were identified, ensuring the absence of the condition of the passivating effect.

Theoretically calculated and confirmed as a result of firing experiments on 75 "Kil0g R AMM0V1XP RSA RBAs The possibility of oxidation of iron, zinc, nickel, cobalt, lead, tin from copper-nickel anodes made from electronic scrap, which ensures high technical and economic indicators of return technology noble metals.

Practical significance of work

A technological line has been developed for the testing of radio-electronic lambs, including separation of disassembly, sorting, mechanical

enrichment of smelting and analyzing of noble and non-ferrous metals;

Developed technology of smelting radio electronic scrap in induction
the oven combined with the impact on the melt of oxidative radial
but-axial jets providing intense mass and heat exchange in the zone
Melting Metal;

Developed and tested in a pilot-industrial scale technolo
Hebic diagram of refining diagrams of electronic leoms and technological
enterprise moves, providing individual processing and calculation with
each supplier RAL.

Approbation of work. The dissertation materials reported: at the International Conference "Metallurgical Technologies and Equipment", April 2003, St. Petersburg; All-Russian scientific-practical conference "New technologies in metallurgy, chemistry, enrichment and ecology", October 2004, St. Petersburg; Annual Scientific Conference of Young Scientists "Mineral Fossils and their development" March 9 - April 10, 2004, St. Petersburg; Annual Scientific Conference of Young Scientists "Merft Fossils of Russia and their development" March 13-29, 2006, St. Petersburg.

Publications. The main provisions of the dissertation are published in 7 printed works, including 3 patents for the invention.

The materials of this paper present the results of laboratory research 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 in industrial conditions of SKIF-3 enterprise at the venues of the Russian Scientific Center "Applied Chemistry" and the Mechanical Plant them. Karl Liebknecht.

Study of the real composition of the radio electronic scrap

Currently, there is no domestic technology for processing poor electronic leoms. Purchase of a license from Western companies inexpresentation in view of incomprehensible laws on precious metals. Western companies may buy electronic suppliers from suppliers, storage and accumulate scrap volume to a value that corresponds to the scope of the process line. The precious metals obtained are the property of the manufacturer.

In our country, according to the terms of cash settlements with the suppliers of scrap, each batch of waste of each serve, regardless of its size, must undergo a complete technological cycle of testing, which includes opening of parcels, testing the masses of the net and gross, averaging of raw materials in composition (mechanical, pyrometallurgical, chemical) selection of head samples , sampling from side products averaging (slags, insoluble precipitation, washwater, etc.), encryption, analysis, transfers of samples and certification of test results, calculation of the number of precious metals in the party, their adoption on the balance of the enterprise and the execution of the entire accounting and settlement documentation.

After receiving concentrated semi-product precales (for example, Metal Dore), concentrates are rented for a state refining plant, where, after affinage, the metals go to Gokhran, and payment for their cost is sent by the reverse financial chain up to the supplier. It becomes apparent that for the successful work of processing enterprises, each supplier party must pass separately from the materials of other suppliers the entire technological cycle.

An analysis of the literature showed that one of the possible ways to averaging radio-electronic scrap is its firing at a temperature that ensures the combustion of plastics included in the RAL, after which SPECA was possible, obtaining an anode with subsequent electrolysis.

Synthetic resins are used for the manufacture of plastics. Synthetic resins, depending on the reaction of their formation, divided into polyme-risen and condensed. Thermoplastic and thermosetting resins are also distinguished.

Thermoplastic resins can be melted repeatedly during re-heating, without losing plastic properties, they include: polyvinilacing-tat, polystyrene, polyvinyl chloride, glycole condensation products with dibasic carboxylic acids, etc.

Thermoreactive resins - when heated, form deflated products, these include phenol-aldehyde and urea-formaldehyde resins, glycerol condensation products with polybustic acids, etc.

Many plastics consist only of polymer, they include: poly-ethylene, polystyrene, polyamide resins, etc. Most plastics (phenoplasts, amiplasts, wood plastics, etc.) In addition to the polymer (binder) may contain: fillers, plasticizers binding curable and staining substances, stabilizers and other additives. The following plastics are used in electrical engineering and electronics: 1. Fenoplasty plastics based on phenoloaldehyde resins. Phenoplasts include: a) cast phenoplasts - cured resin resins, such as bakelite, carbit, neolic, etc.; b) Layered phenoplasts - for example, an extruded product from fabric and resolon resin is called textolite phenol-aldehyde resins are obtained by condensation of phenol, cresol, xylene, alkylphenol with formaldehyde, furfural. In the presence of basic catalysts, resolvent (thermosetting) resins are obtained, in the presence of acidic - novolac (thermoplastic resins).

Technological calculations of the disposal of oblivities

All plastics are mainly consisting of carbon, hydrogen and oxygen with the substitution of the valence additives of chlorine, nitrogen, fluorine. Consider the combustion of textolite as an example. Textolite - a rapid material, is one of the components of the electronic scrap. It consists of pressed cotton fabric impregnated with artificial resolved (formaldehyde) resins. Morphological composition of radiotechnical textolite: - cotton fabric - 40-60% (average - 50%) - Resolved resin - 60-40% (average -50%) gross formula of cotton cellulose [UBF702 (OH) s] s, and resolon resin - (CG H702) -m, where M is the coefficient corresponding to the degree of polymerization. According to literary data, with astiness of the textolite, 8% humidity will be 5%. Chemical composition The textolite in terms of 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 combustion of 1 t / hour of textolite, evaporation of moisture is formed 0.05t / hour and ash 0.08 tons / hour. It comes to burning, t / h: C - 0.554; H - 0.058; 0-0.24; S-0,001, N-0,017. The composition of the ash of the textolite of the brand A, b, p according to the literature data,%: SAO -40.0; Na, K20 - 23.0; MG O - 14.0; RP110 - 9.0; Si02 - 8.0; Al 203 - 3.0; Fe203 -2.7; SO3-0.3. For the experiments, the firing was chosen in the hermetic chamber without air access, for this was made of stainless steel ZMM thick box of 100x150x70 mm with flange fastening of the lid. The cover to the box was attached through asbestos gasket with bolted joints. In the ending surfaces of the box, fitting holes were performed through which the contents of the retort and the removal of gas products of the process were purned by inert gas (N2). As experienced samples, it was used: 1. Panels cleaned from radio elements, 20x20 mm. 2. Black chips from boards (in a natural value of 6x12 mm) 3. The connectors from the textolite (are cut to the size of 20x20 mm) 4. Connectors from thermosetting plastic (sized to size 20x20 mm) The experiment was carried out as follows: 100 g of the test sample was loaded into the retort , closed with a lid and placed in the muffle. The contents were blocked by nitrogen for 10 minutes with a flow rate of 0.05 l / min. Throughout the experience, nitrogen consumption was maintained at 20-30 cm3 / min. Exhaust gases with an alkaline solution were neutralized. The muffle mine was closed by brick and asbestos. The temperature rise was adjusted within 10-15s per minute. Upon reaching 600C, there was an hour excerpt, after which the oven turned off and the retort was removed. During cooling, nitrogen consumption increased to 0.2 l / min. The observation results are presented in Table 3.2.

The main negative factor in the process is very strong, sharp, unpleasant smell, standing out from both the flack itself and from the equipment that is "soaked" by this smell after the first experience.

For the study, a tubular rotating continuous oven with indirect electrical heating with a capacity of 0.5-3.0 kg / h is used. The furnace consists of metal casing (length 1040 mm, diameter 400 mm), lined with refractory bricks. Heaters serve 6 silitic rods with a length of the working part of 600 mm, powered by two RNO-250 voltage variants. The reactor (total length is 1560 mm) is a pipe made of stainless steel with an outer diameter of 89 mm with a lining of porcelain pipe inner diameter of 73 mm. The reactor relies on 4 rollers and is equipped with a drive consisting of an electric motor, gearbox and belt transmission.

To control the temperature in the reaction zone, the thermocouple is used in a set with a portable potentiometer installed inside the reactor. It has previously been adjusted to its indications for direct measurements of the temperature inside the reactor.

A radio electron scrap is loaded into the furnace with a ratio: refined from the radio elements: black chips: textolite connectors: connectors from thermoplastic resin \u003d 60: 10: 15: 15.

The conduct of this experiment was carried out from the assumption that the plastic to its melting would burn, which will ensure the release of metal contacts. It turned out to be unattainable, since the problem of a sharp smell remains, besides, as soon as the connectors reached the temperature zone "300 ° C, the connectors from thermoplastic plastics adhered to the inner surface of the rotating furnace and closed the passage of the entire mass of the electronic scrap. Forced air supply to the furnace, the temperature rise in the adhesion zone did not lead to the possibility of ensuring the firing.

Thermoreactive plastic is also characterized by high viscosity and durability. The characteristic of these properties is that when cooled in liquid nitrogen for 15 minutes, the connectors from thermosetting plastics were divided into anvil with a ten-light hammer, while the destruction of the connectors did not occur. Considering the fact that the number of parts performed from such plastics is small and they will be well cut using a mechanical tool, it is advisable to be their manual disassembly. For example, the cutting or splitting of the connectors along the central axis leads to the release of metal contacts from the plastic base.

The nomenclature of the economic scrap processing of the electron industry covers all the details and components of various units and instruments, in the manufacture of which precious metals are used.

The basis of a product containing precious metals, and, accordingly, their scrap can be made of plastic, ceramics, fiberglass, multilayer material (watiosis) and metal.

The commodity coming from enterprises is sent to pre-disassembly. At this stage, units containing precious metals are extracted from electronic computing machines and other electronic equipment. They constitute about 10-15% of the total mass of the computer. Materials that do not contain precious metals are directed to the extraction of non-ferrous and ferrous metals. Exhaust material containing precious metals (printed circuit board, plug connectors, wires, etc.), sorted to remove gold and silver wires, gold-plated pins of the side connectors of printed circuit boards and other parts with a high content of precious metals. Selected details come directly to the precipitation area of \u200b\u200bprecious metals.

Testing technology for obtaining concentrated gold and silver

Trial of a gold sponge weighing 10.10 g was dissolved in royal vodka, evaporation with hydrochloric acid They got rid of nitric acid and landed metallic gold with a saturated solution of iron (s) sulfate prepared from soluble carbonyl iron dissolved in sulfuric acid. The precipitate was repeatedly washed with boiling with a distilled NS1 (1: 1), water and dissolved gold powder in tsarist vodka cooked from the acids stretched in quartz dishes. The precipitation and flushing operation was repeated and selected a sample for emission analysis, which showed the gold content at the level of 99.99%.

To carry out the material balance, the remains of the samples were selected for analysis (1.39 g of AI) and gold with burned filters and electrodes (0.48 g), irretrievable losses were 0.15 g, or 1.5% of the recycled material . Such a high percentage of losses is due to a small amount of gold involved in the processing and the cost of the latter on debugging analytical operations.

The ingots of the silver isolated from the contacts were dissolved when heated in concentrated nitric acid, the solution was evaporated, cooled and merged with salt crystals. The resulting sediment of the nitrate was washed with a pre-nitric acid was dissolved in water and hydrochloric acid was landed in the form of chloride, the decanted uterine solution was used to work out silver refining technology by electrolysis.

The silver chloride precipitate was washed with 69 nuic acid and water, dissolved in excess of aqueous ammonia and filtered. The filtrate was treated with an excess of hydrochloric acid to the cessation of the formation of precipitate. The latter was washed with cooled water and alkaline melting was allocated with metallic silver, which was crossed with boiling NS1, 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 repeated the entire cycle of silver separation through chloride. After smelting with flux and washing with hydrochloric acid, the ingot twice melted in a pyrograph crucible with intermediate operations for cleaning the surface of hot hydrochloric acid. After that, the ingot was rolled into the plate, the surface of the hot NS1 (1: 1) was crossed and a flat cathode was made to purify silver electrolysis.

Metallic silver was dissolved in nitric acid, brought the acidity of the solution to 1.3% by HnO3 and conducted the electrolysis of this solution with a silver cathode. The operation was repeated, and the resulting metal was spiled in a pyrograph tiglet into a bastard in a mass of 10.60 g. Analysis in three independent organizations showed that the mass fraction of silver in a slope of at least 99.99%.

From a large number of work on the extraction of noble metals from the semi-product, we have selected a method of electrolysis in a solution of copper sulfate.

62 g of metal contacts from the connectors were splashing with a buoy and cast a flat ingot weighing 58.53 g. 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 acidic sulfuric acid solution of copper sulfate, as a result of which 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 in the royal vodka, 1.50 g of gold was isolated and 1.52 g of silver. After burning filters, 0.11 g of gold was obtained. The losses of this metal amounted to 0.6%; irreversible losses of silver - 1.2%. A phenomenon of appearance in a palladium solution (up to 120 mg / l) has been established.

With the electrolysis of copper anodes, the precious metals contained in it are concentrated in the sludge, which falls on the bottom of the electrolysis bath. However, there is a significant (up to 50%) palladium transition into an electrolyte solution. To overlap the start of the loss of Palladium Bila, this work was performed.

The difficulty of extracting palladium from electrolytes is due to their complex composition. Known work on the sorption and extraction processing of solutions. The purpose of the work is to obtain pure palladium villages and return the purified electrolyte into the process. To solve the task, we use the process of sorption of metals on the synthetic ion exchange fiber AMPAP H / SO4. Two solutions were used as the starting solutions: No. 1 - containing (g / l): palladium 0.755 and 200 sulfuric acid; №2 - containing (g / l): palladium 0.4, copper 38.5, iron - 1.9 and 200 sulfuric acid. To prepare the sorption column weighed 1 gram of AMPA fiber, placed in a column with a diameter of 10 mm and washed the fiber for 24 hours in water.

Development of palladium extraction technology from sulfur solutions

The supply of the solution was carried out from below using the dosing pump. During the experiments, the volume of the missed solution was recorded. Samples selected at equal intervals of the time, the atomic adsorption method was analyzed for palladium content.

The results of the experiments showed that palladium sorbed on the fiber de-sorbitated with a solution of sulfuric acid (200 g / l).

Based on the results obtained in the study of the sorption processes of Palladium on the solution No. 1, experience was carried out to study the behavior of copper and iron in quantities close to the content of them in the electrolyte, during the sorption of palladium on the fibers. Experiments were carried out according to the scheme shown in Fig. 4.2 (Table 4.1-4.3), which includes the process of sorption of palladium from solution No. 2 on fiber, flushing palladium from copper and iron with a solution of 0.5 m sulfuric acid, palladium desorption with a solution of 200 g / L sulfuric acid and flushing with water fiber (Fig.4.3).

As starting raw materials, enrichment products obtained on the enrichment site of the enterprise "SKIF-3" took place. Melting was carried out in the Tamman furnace at a temperature of 1250-1450s in graphite-shamotovy triggers of 200 g (copper). Table 5.1 presents the results of laboratory floats of various concentrates and their mixtures. Concentrates were melted without complications, the compositions of which are presented in Tables 3.14 and 3.16. The concentrates, which are presented in Table 3.15, require a temperature in the interval 1400-1450c for melting. The mixtures of these materials L-4 and L-8 require a temperature of about 1300-1350c for melting.

Industrial smelting P-1, P-2, P-6, carried out in an induction furnace with a crucible capacity of 75 kg on copper, confirmed the possibility of melting concentrates, when the gross composition of enriched concentrates was supplied on the melting.

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 RAL capacitors, Table 3.14). The mechanism of losses was determined by adding contacts to the surface of the copper molten bath with surface spraying on them silver and palladium (palladium content in contacts 8.0-8.5%). In this case, copper with silver was paid, leaving the palladium shell of contacts on the surface of the bath. An attempt to enjoy palladium in the bath led to the destruction of the shell. Part of the palladium flew off the surface of the crucible, did not have time to dissolve in a copper bath. Therefore, all subsequent smelting was carried out with a coating synthetic slag (50% S1O2 + 50% soda).

Kozyrev, Vladimir Vasilyevich

Abstract of dissertation. on the topic "Development of an effective technology for extracting non-ferrous and noble metals from the waste of the radio engineering industry"

For manuscript rights

Veliakov Aleksey Nail'evich

Development of effective technology

Extract of non-ferrous and noble metals from the waste of the radio engineering industry

Specialty 05.16.02 - Metallurgy black, color

St. Petersburg 2007

The work was implemented in the State Educational Institution of Higher Professional Education of the St. Petersburg State Mountain Institute named after GV Plakhanov (Technical University).

Scientific supervisor --Odtor of Technical Sciences, Professor, Honored Scientist of the Russian Federation

The leading enterprise is the Institute "Gipronicel".

The defense of the thesis will take place on November 13, 2007 at 14 h 30 min at the meeting of the dissertation council D 212.224.03 at St. Petersburg State Mountain Institute named after G.V. Plakhanov (Technical University) at the address: 199106 St. Petersburg, 21st Line , D.2, Aud. 2205.

The dissertation can be found in the library of the St. Petersburg State Mining Institute.

Sizyakov V.M.

Official opponents: Doctor of Technical Sciences, Professor

Beloglase I.N.

candidate of Technical Sciences, Associate Professor

Baymakov A.Yu.

SCIENTIFIC SECRETARY

dissertation council D.N., Associate Professor

V.N.brichkkin

GENERAL DESCRIPTION OF WORK

Relevance of work

Modern technology needs increasing amounts of noble metals. Currently, the production of the latter has decreased dramatically and does not provide needs, therefore it is necessary to use all the possibilities for mobilizing the resources of these metals, and, therefore, the role of secondary metallurgy of noble metals is increasing in addition to the extraction of AI, AG, P1 and PC1 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, led to the need to create in certain regions of the country's market for the processing of scrap of radio-electronic industry containing precious metals with the maximum extraction of precious metals from poor raw materials and a decrease in the residue tails is also important is also The fact that along with the extraction of precious metals can be obtained additionally non-ferrous metals, for example, copper, nickel, aluminum and others

Purpose of work. Improving the efficiency of pyro-hydrometallurgical technology for processing the scrap of radio-electronic industry with deep extraction of gold, silver, platinum, palladium and non-ferrous metals

Research methods. To solve the tasks set, the main experimental studies were carried out at the original laboratory setup, including a furnace with radially located blowing nozzles, allowing to ensure the rotation of the molten metal with air without splashing and due to this, to repeatedly increase the flow of the blast (in comparison with the air supply to the molten metal through the pipes). Analysis of enrichment products, smelting, electrolysis was carried out by chemical methods. For the study used the X-ray method

thrust microanalysis (RSMA) and X-ray phase analysis (RFA).

The accuracy of scientific provisions, conclusions and recommendations is due to the use of modern and reliable research methods and is confirmed by the good convergence of theoretical and practical results.

Scientific novelty

The main qualitative and quantitative characteristics of radiole elements containing non-ferrous and precious metals are determined, allowing to predict the possibility of chemical and metallurgical processing of radio-electronic scrap

The passivating effect of lead oxide films under electrolysis of copper-nickel anodes made from electronic scrap is established. The composition of the films was revealed and technological conditions for the preparation of anodes, ensuring the absence of a passivating effect

Theoretically calculated and confirmed as a result of firing experiments on 75 kilogram melt samples The possibility of iron, zinc, nickel, cobalt, lead, tin from copper-nickel anodes made from electronic scrap, which ensures high technical and economic indicators of the reproduction technology of noble metals The magnitude of the apparent activation energy for oxidation in the copper alloy lead - 42.3 kJ / mol, tin - 63,1 kJ / mol, iron 76.2 kJ / mol, zinc - 106.4 kJ / mol, nickel - 185.8 kJ / mole.

A technological line has been developed for the testing of radio-electronic leoms, including separation of disassembly, sorting and mechanical enrichment to obtain metal concentrates,

Developed technology of smelting radio electronic scrap in an induction furnace, combined with the impact on the oxide melt

radial-axial jets providing intense mass and heat exchange in the metal melting area,

The novelty of technical solutions was confirmed by three patents of the Russian Federation No. 2211420, 2003; № 2231150, 2004, № 2276196, 2006

Approbation of work The dissertation materials 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 "Useful Fossils of Russia and their development" March 9 - April 10, 2004. Saint-Petheraggrag, Annual Scientific Conference of Young Scientists "Merft Russia and their development" March 13-29, 2006 St. Petersburg

Publications. The main provisions of the dissertation were published in 4 printed works

Structure and scope of the dissertation. The thesis consists of the introduction, 6 chapters, 3 applications, conclusions and literature of the literature The work is set out on 176 pages of machine-written text, contains 38 tables, 28 drawings Bibliography includes 117 names

In the introduction, the relevance of research is substantiated, the main provisions endowed with

The first chapter is devoted to the review of the literature and patents in the field of technology for the processing of radio electronic industries and methods of processing products containing precious metals based on the analysis and generalization of literary data formulated the objectives and objectives of research

The second chapter provides data on the study of the quantitative and real composition of the radio electronic scrap

The third chapter is devoted to the development of averaging technology of radio-electronic scrap and obtaining metal concentrates of RAL enrichment.

In the fourth chapter, data on the development of technology for obtaining metal concentrates of radio-electronic scrap with the extraction of noble metals

The fifth chapter describes the results of semi-industrial tests for fusing metal concentrates of radio-electronic scrap, followed by processing on cathode copper and slurry of noble metals

The sixth chapter discusses the possibility of improving technical and economic indicators of processes developed and proven in a pilot-industrial scale.

Basic Protected Provisions

1. Physico-chemical studies of many varieties of radio-electronic scrap substantiate the need for preliminary disassembly disassembly of waste sorting with subsequent mechanical enrichment, which ensures rational processing technology of the resulting concentrates with the release of non-ferrous and noble metals.

Based on the study of scientific literature and preliminary studies, the following heads of refining operations of electronic leomov-1 were reviewed and tested. Mocking scrap in electric furnace,

2 leaching of scrambles in solutions of acids;

3 Lomom firing, followed by electric fusion and electrolysis of semi-finished products, including non-ferrous and noble metals,

4 Physical enrichment of Lomoms, followed by electric melting on the anodes and processing anodes on cathode copper and sludge of noble metals.

Three first ways were rejected due to environmental difficulties that are irresistible when using the head operations under consideration.

The method of physical enrichment was developed by us and is that the incoming raw material is sent to pre-disassembly at this stage of electronic computing machines and other electronic equipment, nodes containing precious metals (Tables 1, 2) materials that do not contain precious metals are retrieved to extract non-ferrous metals Material containing precious metals (printed circuit board, plug connectors, wires, etc.) is sorted to remove gold and silver wires, gold-plated pins of the side connectors of printed circuits and other parts with a high content of precious metals. These parts can be recycled separately

Table 1

Balance of electronic equipment on the site of the 1st disassembly

No. P / p Prombroduct Name Number, CG Content,%

1 It has come for processing electronic devices, machines, switching equipment 24000.0 100

2 3 Received after processing Electronic scrap in the form of boards, connectors, etc. Scrap of non-ferrous and ferrous metals, not containing noble metals, plastic, organic glass Total 4100.0 19900.0 17.08 82.92

table 2

Balance of electronic scrap on a plot of 2nd disassembly and sorting

p / p Promproduct name

, kg Nie,%

Received for processing

1 electronic scrap (connectors and boards) 4100.0 100

Received after the manual separation

disassembly and sorting

2 connectors 395.0 9,63

3 radio components 1080.0 26.34

4 boards without radio components and accessories (on WPP 2015.0 49,15

jannoe legs of radio components and on the semi

hold noble metals)

Latches of boards, pins, guide boards (ele-

5 cops do not contain noble metals) 610.0 14.88

TOTAL 4100.0 100.

Parts such as connectors on thermosetting and thermoplastic base, connectors on boards, small boards from getancase or fiberglass with separate radio components and tracks, condensers of variable and constant tank, microcircuits on a plastic and ceramic based, resistors, ceramic and plastic sockets radiolmp , fuses, antennas, switches and switches, can be recycled by enrichment.

As a head unit for crushing operation, a hammer crusher MD 2x5 was tested, a cheek crusher (tenant 100x200) and a cone-inertial crusher (KID-300)

In the process, it turned out that the cone inertial crusher should only work under the root of the material, the TE with the full filling of the receiving funnel. For efficient work The conical inertial crusher exists the upper limit of the size of the processable material of the larger sizes violates the normal operation of the crusher. These shortcomings, the main of which is the need for mixing materials of different

suppliers, forced to abandon the use of KID-300 as a head unit for grinding.

The use of a hammer crusher as a head grinding unit in comparison with the cheek turned out to be more preferable due to its high performance when crushing electronic scrap

It has been established that crushing products include magnetic and non-magnetic metal fractions that contain the bulk of gold, silver, palladium. To remove the magnetic metal part of the grinding product, the magnetic separator of the PBSC 40/10 was tested that the magnetic part mainly consists of nickel, cobalt, iron (Table 3) determined the optimal performance of the device, which was 3 kg / min at the extraction of gold 98.2 %

The non-magnetic metal part of the crushed product was highlighted using the SB 32/50 electrostatic separator, it was found that the metal part consists mainly of copper and zinc. The noble metals are represented by silver and palladium. The optimal performance of the device was determined, which was 3 kg / min with a silver extraction of 97.8%.

When sorting the radio electronic scrap, it is possible to selectively selection of dry multilayer capacitors, which are characterized by an increased platinum content - 0.8% and palladium - 2.8% (Table 3)

Table 3.

The composition of the concentrates obtained by sorting and processing radio-electronic scrap

C number with 1xx re screw AI RS1 14 Other

1 2 3 4 5 6 7 8 9 10 11 12

Silver-palladium concentrates

1 64.7 0.02 CL 21.4 OD 2.4 CL 0.3 0.006 11.8 100.0

2 77,3 0,7 0,03 4,5 0,7 0,3 1,3 0,5 0,01 19,16 100,0

Magnetic concentrates

3 Sl 21.8 21.5 0.02 36.3 CL 0.6 0.05 0.01 19.72 100.0

Concentrates from condensers

4 0.2 0.59 0,008 0.05 1.0 0.2 No 2.8 0.8 m £ 0-14.9 SAO-25,6 8P-2.3 Р Л-2,5,1203-49, 5 100.0

Figure 1 Agsharate-technological scheme for enrichment of radio electronic scrap

1- hammer crusher MD-2X5; 2-crusher Tooth-roll 210 Dr., 3-vibrationrochot VG-50, 4-Magggo Separator PBSC-40 / Yu; 5- Separator Elektostatic SB-32/50

2. The combination of the process of melting concentrates of REL and electrolysis of the obtained medical-nickel anodes is based on the technology of concentration of noble metals in sklyts suitable for processing with standard methods; To improve the efficiency of the method at the stage of smelting, placing the impurities of the RAL in the devices with radial-but-sized velocked nozzles.

The physico-chemical analysis of the details of the radio 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-M50 50-40.

Concentrates of Ral Shoy

.......................... ■ .- ... i ii. "H

Leaching

hgpulpa

Filtration

I Solution I sediment (AI, VP, Hell, SI, N1) - ■ on production Ai

AG deposition

Filtration

Solution for utilization ^ SI + 2, M + 2.2P + \\ RSG2

"Tad on alkaline ▼ pl

Figure 2 Diagram of extraction of noble metals with leaching of concentrate

Since most of the concentrates obtained during sorting and enrichment are represented in metallic form, the extraction scheme with leaching in acid solutions was tested. The diagram shown in Figure 2 was tested to give gold with a purity of 99.99% and silver 99.99%. Removing gold and silver amounted to 98.5% and 93.8%, respectively. To extract palladium from solutions, the process of sorption on synthetic ion-exchange fiber AMPAN N / 804 was investigated.

The sorption results are presented in Figure 3. The sorption-native fiber container was 6.09%.

Fig.3. Results of palladium sorption on synthetic fiber

High aggressiveness of mineral acids, relatively low recovery of silver and the need to utilize a large number of reset solutions narrows the possibility of using this method to process gold concentrates (the method is ineffective for the processing of the entire volume of radio-electronic scrap concentrates).

Since the concentrates on a copper basis quantitatively predominate in concentrates (up to 85% of the total mass) and the copper content in these concentrates is 50-70%, in laboratory level

the possibility of refining concentrate based on melting on copper-nickel anodes was tested, followed by their dissolution.

Concentrates of radio-electronic scrap

Electrolyte I- \\

- [Electrolysis |

Slut noble cathode metal copper

Fig.4 Diagram of extraction of noble metals with melting on copper-nickel anodes and electrolysis

The melting of the concentrates was carried out in the "Tamman" furnace in the graph-shamotovy triggers, the mass of melting was 200 g without complications melted copper-based concentrates. The temperature of their melting is in the range of 1200-1250 ° C. The concentrates on the iron and nickel-based basis require for melting the temperature of 1300-1350 ° C industrial smelting, carried out at a temperature of 1300 ° C in an induction furnace with a crucible 100 kg, confirmed the possibility of melting concentrates when the gross composition of enriched concentrates is supplied.

contains 40 g / l of copper, 35 g / l H2804. The chemical composition of the electrolyte, sludge and cathode sediment are shown in Table 4

As a result of the tests, it was established that with the electrolysis of the anodes made from the metallic fractions of the electronic scrap alloy, the electrolyte used in the electrolysis bath is impoverished on copper, it is accumulated in it as nickel impurities, zinc, iron, tin.

It has been established that palladium under electrolysis conditions is divided into all electrolysis products, so, in the electrolyte, the palladium content is up to 500 mg / l, the concentration on the cathode reaches 1.4% the smaller part of the palladium enters the sludge. In the sludge, tin is accumulated, which makes it difficult to recycle it without pre-withdrawal Tin Tin turns into the sludge and it also makes it difficult to process it with a passivation of the anode X-ray structural and chemical analysis of the upper part of passivated anodes showed that the cause of the observed phenomenon is lead oxide.

Since the lead present in the anode is in metallic form, the following processes occur on the anode.

Ry - 2e \u003d p2 +

20n - 2e \u003d H20 + 0.502 804 "2 - 2e \u003d 8<Э3 + 0,502

With a minor concentration of fistula ions in a sulfur electrolyte, its normal potential is the most negative, so lead sulfate is formed on the anode, which reduces the anode area, as a result of which an anode current density increases, which contributes to the oxidation of bivalent lead in tetravalent ions

Ry2 + - 2e \u003d pi4 +

As a result of hydrolysis, the formation of RU2 is based on the reaction.

Rye (804) 2 + 2N20 \u003d РИ02 + 2N2804

Table 4.

The results of dissolving anodes

№ PP Product Name Content,%, g / l

C number with HP Be Mo R<1 Аи РЬ Бп

1 Anode,% 51.2 11.9 1.12 14.4 12.4 0.5 0.03 0.6 0.15 3.4 2.0 2.3

2 cathode sediment,% 97.3 0.2 0.03 0,24 0.4 No Slim 1.4 0.03 0.4 No No

3 electrolyte, g / l 25.5 6.0 0.4 9.3 8.8 0.9 CL 0.5 0.001 0,5 No 2.9

4 sludge,% 31.1 0.3 Sl 0.5 0.2 2.5 CL 0.7 1.1 27,5 32.0 4.1

Lead oxide creates a protective layer on the anode, which determines the impossibility of further dissolution of the anode. The electrochemical potential of the anode was 0.7 V, which leads to the transfer of palladium ions to the electrolyte and the subsequent discharge of it on the cathode

The supplement of chlorine ion to the electrolyte allowed to get away from the pheniization phenomenon, but it did not solve the issue of electrolyte utilization and did not provide the application of the standard processing technology of sailed

The results obtained showed that the technology ensures the processing of radio-electronic scrap, but it can be significantly improved under the condition of oxidation and instead of impurities of a group of metals (nickel, zinc, iron, tin, lead) of the radio electronic scrap during concentrate melting.

Thermodynamic calculations carried out from the assumption that the oxygen of the furnace in the bath tub, showed that such impurities, as BE, HP, A1, BP and PI, can be oxidized in copper thermodynamic complications during oxidation. Residual nickel concentrations occur with nickel - 9 , 37% when the copper content in the copper melt is 1.5% CI20 and 0.94% when the content in the melt is 12.0% CI20.

Experimental check was carried out on a laboratory furnace with a mass of 3 kg of copper with radially located blowing nozzles (Table 5), allowing to ensure the rotation of the molten metal by air without splashing and due to this repeatedly increase the flow of the blast (in comparison with the air supply to the molten metal through the pipes )

Laboratory studies have been established that an important role in the oxidation of the metal concentrate belonging to ... 4 The composition of the slag during melting with fluxe quartz does not switch to the tin slag and it makes it difficult to switch the lead when using a combined flux consisting of 50% of quartz sand and 50% of soda, go to slag All impurities

Table 5.

The results of the melting of the metal concentrate of waste electronic scrap with radially located blowing nozzles depending on the purge time

№ PP Product Name Composition,%

C number re GP RL BP Hell Ai M Other

1 alloy source 60.8 8.5 11.0 9.5 0.1 3.0 2.5 4.3 0.10 0.2 0,0 100.0

2 Alloy after a 15-minute purge 69.3 6.7 3.5 6.5 0.07 0.4 0.8 4,9 0.11 0.22 7.5 100.0

3 Alloy after a 30-minute purge 75.1 5.1 0.1 4.7 0.06 0.3 0.4 5.0 0.12 0.25 8.87 100.0

4 Alloy after a 60-minute purge 77.6 3,9 0.05 2.6 0.03 0.2 0.09 5.2 0.13 0.28 9.12 100.0

5 Alloy after 120-minute purge 81.2 2.5 0.02 1.1 0.01 0.1 0.02 5.4 0.15 0.30 9.2 100.0

The results of the melting show that 15 minutes of blowing through blowing nozzles are sufficient to remove a significant part of impurities. The apparent activation energy of oxidation reaction in the copper alloy lead is 42.3 kJ / mol, tin -63,1 kJ / mol, iron 76.2 kJ / mol, zinc - 106.4 kJ / mol, nickel - 185.8 kJ / Mol

Studies on the anodic dissolution of smelting products have shown that the passivation of the anode with the electrolysis of the alloy in the sulfate electrolyte is missing after a 15-minute purge. The electrolyte is not impoverished by copper and is not enriched with impurities in the sludge when weaving impurities, which ensures its multiple use in the sludges there are no lead and tin, which allows you to use the standard sludge processing technology according to the sludge stroke scheme - »Alkaline melting on gold-silver alloy

According to the results of studies, oven aggregates with radially located blowing nozzles, operating in periodic mode by 0.1 kg, 10 kg, 100 kg of copper, ensuring the processing of various batches of radio-electronic scrap, with the same technological processing line exercise the extraction of precious metals without unification Parties of various suppliers, which provides accurate financial calculation for the metals for the test results, the initial data was developed for the construction of a ral processing plant with a capacity of 500 kg of gold per year, a project of an enterprise was completed for the payback period of capital investments 7-8 months

1 Developed theoretical foundations of the method of processing the waste of the radio electronic industry with deep extraction of noble and non-ferrous metals.

1 1 The thermodynamic characteristics of the main metal oxidation processes in the copper alloy are determined, allowing to predict the behavior of the mentioned metals and impurities

1 2 Defined the values \u200b\u200bof the apparent oxidation activation energy in the copper alloy of nickel - 185,8 kJ / mol, zinc -106.4 kJ / mol, iron - 76.2 kJ / mol, tin 63.1 kJ / mol, lead 42.3 KJ / mol.

2 Developed a pyrometallurgical technology for processing the wastes of the radio electronic industry to obtain a gold-silver alloy (metal expensive) and platinum-palladium concentrate.

2.1 Installed technological parameters (crushing time, productivity of magnetic and electrostatic separation, the degree of extraction of metals) of the physical enrichment of REL under the grinding scheme - »Magnetic separation -» Electrostatic separation, which allows to obtain concentrates of noble metals with predicted quantitative and qualitative composition

2 2 The technological parameters (melting point, air flow, the degree of transition of impurities in the slag, the composition of the refining slag) of the oxidative melting of the concentrates in the induction furnace with the supply of air to the air of the air with radial-axial furms are determined; Aggregates with radial-axial trucks of various performance are developed and tested.

3 On the basis of the studies conducted and launched in the production of an experimental plant for the processing of electron electron scrap, comprising a grinding section (MD2x5 crusher), magnetic and electrostatic separation (PBSC 40/10 and SB 32/50), melting in an induction furnace (PI 50 / 10) with an account 1-60 / 10 generator and a melting unit with radio-butter-axial trucks, electrochemical dissolution of the anodes and processing of flames of noble metals, the effect of "passivation" of the anode was investigated, the existence of sharply extreme dependence of the lead content in copper-nickel anode was established made from electronic scrap, which should be taken into account when controlling the process of oxidative radial-axial melting

4. As a result of semi-industrial tests of radio-electronic scrap processing technology, source data

for the construction of a factory for the processing of waste radiotechnical industry

5. The expected economic effect of the introduction of the development of the dissertation in the calculation of the Gold capacity of 500 kg / year is ~ 50 million rubles. With payback period of 7-8 months

1 Tellyakov A.No utilization of waste electrotechnical enterprises / An Thalkov, D.V. Gorlenkov, E.Yu Stepanova // Abstracts of the report of the international report. Con "Metallurgical Technologies and Ecology" 2003

2 Tellakov A N. Results of testing technology of refining radio electronic scrap / AN Tranki, L.V. Sikonin // Notes of the Mining Institute. T 179 2006.

3 Telikov A.N Research on the oxidation of impurities of the ME-Talloconcentrate of radio electronic scrap // Notes of the Mining Institute T 179 2006

4 Telikov A.N. Technology of recycling of the Radio Electronic Industry / An Thalkov, D V.Gorlenkov, E.Yu Georgiev // Color Metals No. 6 2007.

RIC SNGGI 08 109 2007 3 424 T 100 EKS 199106 St. Petersburg, 21st Line, d 2

Introduction

Chapter 1. Review of literature.

Chapter 2. Study of the real composition

Radioelectronic scrap.

Chapter 3. Development of averaging technology

Radioelectronic scrap.

3.1. Firing radio electronic scrap.

3.1.1. Plastic information.

3.1.2. Technological calculations of the disposal of oblique gases.

3.1.3. Firing of radio electronic scrap in air deficiency.

3.1.4. Firing of radio-electronic scrap in a tubular furnace.

3.2 Physical methods for processing radio-electronic scrap.

3.2.1. Description of the processing plot.

3.2.2. Technological scheme of the enrichment site.

3.2.3. The development of enrichment technology on industrial units.

3.2.4. Determination of the productivity of the aggregates of the enrichment section in the processing of radio-electronic scrap.

3.3. Industrial trials of enrichment of radio electronic scrap.

3.4. Conclusions to the 3 chapter.

Chapter 4. Development of technology for processing concentrates of radio-electronic scrap.

4.1. Research for the processing of RAL concentrates in acid solutions.

4.2. Turning the technology of obtaining concentrated gold and silver.

4.2.1. Testing the technology of obtaining concentrated gold.

4.2.2. Testing the technology of obtaining concentrated silver.

4.3. Laboratory studies on the extraction of gold and silver REL fuscoach and electrolysis.

4.4. Development of palladium extraction technology from sulfuric acid solutions.

4.5. Conclusions to chapter 4.

Chapter 5. Semi-industrial melting tests and electrolysis of concentrates of radio-electronic scrap.

5.1. Melting Metal Concentrate Ral.

5.2. Electrolysis Melting products RAL.

5.3. Conclusions to 5 chapter.

Chapter 6. Studying the oxidation of impurities when smelting radio-electronic scrap.

6.1. Thermodynamic calculations of the oxidation of RAL impurities.

6.2. Study of the oxidation of impurities of RAL concentrates.

6.3. Semi-industrial tests for oxidative welding and electrolysis of RAL concentrates.

6.4. Conclusions on the chapter.

Introduction 2007, thesis on metallurgy, calves, Alexey Nailievich

Relevance of work

Modern technology needs increasing amounts of noble metals. Currently, the prey of the latter declined sharply and does not provide needs, so it is necessary to use all the possibilities for mobilizing the resources of these metals, and, therefore, the role of secondary metallurgy of noble metals is increasing. In addition, the extraction of AU, AG, PT and PDs contained in waste is more profitable than from ores.

Changing the economic mechanism of the country, including the military-industrial complex and armed forces, led to the need to create in certain regions of the country's processing complexes for the scrap of electronic industries containing precious metals. In this case, the maximum extraction of precious metals from poor raw materials and a decrease in the mass of residual tailings is obligatory. It is also important that along with the extraction of precious metals, non-ferrous metals can be obtained, for example, copper, nickel, aluminum and others.

The aim of the work is to develop technology for the extraction of gold, silver, platinum, palladium and non-ferrous metals from the leoms of the radio electronic industry and technological waste of enterprises.

The main provisions endowed

1. Pre-sorting of REL followed by mechanical enrichment provides metal alloys with increased extraction in them of precious metals.

2. Physico-chemical analysis of the details of the radio 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-y0.

3. Low potential for the dissolution of copper-nickel anodes obtained by smelting of radio electronic scrap ensures the possibility of obtaining sludges of noble metals suitable for processing according to standard technology.

Research methods. Laboratory, enlarge-laboratory, industrial tests; Analysis of enrichment products, smelting, electrolysis was carried out by chemical methods. For the study, the method of x-ray microanalysis (RSMA) and X-ray phase analysis (RFA) was used using the Dron-O setup.

The validity and accuracy 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 comprehensive research performed in laboratory, consolidated-laboratory and industrial conditions.

Scientific novelty

The main qualitative and quantitative characteristics of radiole elements containing non-ferrous and precious metals are determined to predict the possibility of chemical and metallurgical processing of radio-electronic scrap.

The passivating effect of lead oxide films under electrolysis of copper-nickel anodes made from electronic scrap is established. The composition of the films was revealed and technological conditions for the preparation of the anodes were identified, ensuring the absence of the condition of the passivating effect.

Theoretically calculated and confirmed as a result of firing experiments on 75-kilogram melt samples The possibility of iron, zinc, nickel, cobalt, lead, tin from copper-nickel anodes made from electronic scrap, which ensures high technical and economic indicators of the technology of return of noble metals.

Practical significance of work

A technological line has been developed for the testing of radio-electronic leoms, including separation of disassembly, sorting, mechanical enrichment of melting and analyzing noble and non-ferrous metals;

The technology of smelting of electronic scrap in an induction furnace, combined with the impact on the melt of oxidative radial-n-axial jets, providing intense mass and heat exchange in the metal melting zone;

The technological scheme of the processing of radio-electronic leoms and technological waste of enterprises, providing individual processing and calculation with each REL supplier, was developed and tested in a pilot-industrial scale.

Approbation of work. The dissertation materials reported: at the International Conference "Metallurgical Technologies and Equipment", April 2003, St. Petersburg; All-Russian scientific-practical conference "New technologies in metallurgy, chemistry, enrichment and ecology", October 2004, St. Petersburg; Annual Scientific Conference of Young Scientists "Mineral Fossils and their development" March 9 - April 10, 2004, St. Petersburg; Annual Scientific Conference of Young Scientists "Merft Fossils of Russia and their development" March 13-29, 2006, St. Petersburg.

Publications. The main provisions of the dissertation are published in 7 printed works, including 3 patents for the invention.

The materials of this paper present the results of laboratory research 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 in industrial conditions of SKIF-3 enterprise at the venues of the Russian Scientific Center "Applied Chemistry" and the Mechanical Plant them. Karl Liebknecht.

Conclusion thesis on the topic "Development of effective technology for the extraction of non-ferrous and noble metals from the waste of the radio engineering industry"

Conclusions for work

1. Based on the analysis of literary sources and experiments, a perspective method for processing radio-electronic scrap, including sorting, mechanical enrichment, melting and electrolysis of copper-nickel anodes was revealed.

2. Developed a technology for testing radio-electronic scrap, allowing to recycle separately each technological batch of the supplier with quantitative determination of metals.

3. On the basis of comparative tests of 3 head chopper vehicles (cone-inertial crusher, a cheek crusher, a hammer crusher), a hammer crusher is recommended for industrial implementation.

4. On the basis of the research conducted and launched an experimental plant for the processing of radio-electronic scrap.

5. In laboratory and industrial experiments, the "Passivation" effect of the anode was investigated. The existence of a sharply extreme dependence of the lead content in the copper-nickel anode made from electronic scrap is established, which should be taken into account when controlling the process of oxidative radial-axial melting.

6. As a result of semi-industrial tests of radio electronic scrap processing technology, source data has been developed for the construction of a plant for the processing of radiotechnical waste.

Bibliography Calves, Alexey Nail, thesis on the topic Metallurgy black, colored and rare metals

1. Mermetukov MA Metallurgy of noble metals / M.A.methettukov, A.M. Orlov. M.: Metallurgy, 1992.

2. Swan I. Problems and the possibility of recycling secondary raw materials containing noble metals. The theory and practice of non-ferrous metallurgy processes; Experience of metallurgists I. Bed, S.Sigenbalt, Krolo, L. Shloss. M.: Metallurgy, 1987. P. 74-89.

3. Malhotra S. RECLAMATION OF PRECIOUS METALS FOR SERAP. In Precious Metals. MINING EXTRACTION AND PROCESSING. Proc. Int. SUMP. LOS-ANGELES FERBER 27-29.1984 MET. SOC. Of aume. 1984. P. 483-494

4. Williams D.P., Drake P. Recovery of Precious Metals from Electronic SCRAP. Proc GTH int Precious Metals Conf. NewPort Beach, Calif. IUNE 1982. Toronto, Pergamon Press 1983 p 555-565.

5. DOVE R DEGUSSA: A Diversified Specialist. Metal Bull Mon 1984 №158 p.ll, 13, 15, 19,21.

6. GOLD FROM GARHOGE. The Northern Miner. V. 65. №51. P. 15.

7. Dunning B.W. Preciouus Metals Recovery From Electronic Scrap and Solder Used in Electronic Manufacture. INT CIRC BUREAU OF MINES US DEP. INTER 1986 №9059. P. 44-56.

8. Egorov V.L. Magnetic electrical and special methods of enrichment of ores. M.: Subraser 1977.

9. Angels A.I. Physical bases of electrical separation / A.I.ANgelov, I.P. Mer.The. M .: Nedra. 1983.

10. Maslenitsky I.N. Metallurgy of noble metals / I.N. Maslenitsky, L.V. Chugaev. M.: Metallurgy. 1972.

11. Basics of metallurgy / edited by N.S.Graver, I.P. SAZHINA, I.A.Strigriry, A.V. Troitsky. M.: Metallurgy, T.V. 1968.

12. Smirnov V.I. Metallurgy copper and nickel. M.: Metallurgy, 1950.

13. Morrison B.h. Recovery of Silver And Gold from Refinery Slimes AT Canadian Copper Refiners. In: Proc Symp Extraction MetallureGy 85. London 9-12 Sept 1985 Institute of Mininy and Metall London 1985. P. 249-269.

14. LEIGH A.H. The Practice of Thin Refining Of Precions Metals. Proc. Int Symp HydrometallureGy. Chicago. 1983 FeBr. 25 MARCHL - AIME, NY - 1983. P.239-247.

15. Technical conditions TU 17-2-2-90. Silver-gold alloy.

16. GOST 17233-71 -Gost 17235-71. Methods of analysis.

17. Analytical chemistry of platinum metals / ed. Acad

18. A.P. Vinogradova. M.: Science. 1972.

19. Pat. RF 2103074. A method for extracting noble metals from golden sands / V.A. Enerlov et al. 1991.08.01.

20. Pat. 2081193 RF. The method of percolation extraction of silver and gold from ores and dumps / Yu.M.Potashnikov et al. 1994.05.31.

21. Pat. 1616159 RF. Method for extracting gold from clay ore /

22. B.K. Chernov et al. 1989.01.12.

23. Pat. 2078839 RF. Flotokoncentratrate Recycling Line / A.F.Panchenko et al. 1995.03.21.

24. Pat. 2100484 RF. The method of obtaining silver from its alloys / A.B. Bed, V.I. Skorodov, S.S. Nabyuchenko et al. 1996.02.14.

25. Pat. 2171855 RF. A method for extracting platinum metals from sailed / N.I.Timofeev et al. 2000.01.05.

26. Pat. 2271399 RF. The method of leaching palladium from sludge / A.R.Tatarinov et al. 2004.08.10.

27. Pat. 2255128 RF. The method of extraction of palladium from waste / Yu.V. Deemin et al. 2003.08.04.

28. Pat. 2204620 RF. The method of processing precipitation based on iron oxides containing noble metals / Yu.A. Sididenko et al. 1001.07.30.

29. Pat. 2286399 RF. The method of processing materials containing noble metals and lead / A.K.Ter-Oganeyanz et al. 2005.03.29.

30. Pat. 2156317 RF. Method for extracting gold from gold-containing raw materials / V.G.Moisesenko, V.S. Rimkevich. 1998.12.23.

31. Pat. 2151008 RF. Installation for the extraction of gold from industrial waste / N.V. Doves, V.A.Prokopenko. 1998.06.11.

32. Pat. 2065502 RF. The method of extraction of platinum metals from the material containing them / A.V. Ermacov et al. 1994.07.20.

33. Pat. 2167211 RF. Environmentally friendly method for extracting noble metals from materials containing them / V.A.Gurov. 2000.10.26.

34. Pat. 2138567 RF. The method of extracting gold from gilded parts containing molybdenum / S.I.Loleit et al. 1998.05.25.

35. Pat. 2097438 RF. Method for extracting metals from waste / Yu.M. Sisovoev, A.G.Irisov. 1996.05.29.

36. Pat. 2077599 RF. The method of isolating silver from waste containing heavy metals / A.G. Kastov et al. 1994.07.27.

37. Pat. 2112062 RF. The method of processing of shlik gold / A.I. Karpukhin, I.I. Selnina, G.S. Yebkin. 1996.07.15.

38. Pat. 215120 RF. The method of recycling alloy of ligatural gold /

39. A.I. Karpukhin, I.I. Selnina, L.A. Medvedev, D.E. DEMENTEV. 1998.11.24.

40. Pat. 2115752 RF. The method of pyrometallurgical refining of platinum alloys / A.G. Maazaletsky, A.V. Ermacov, etc. 1997.09.30.

41. Pat. 2013459 RF. Method of refining silver / E.V. Lapitskaya, M.G.Slotintseva, E.I. Yervin, N.M. Sloity. E.M. Beschkov, N.M.Trefimov, 1. B.P.Nikitin. 1991.10.18.

42. Pat. 2111272 RF. The method of isolating platinum metals. V.I.Shortyov, etc. 1997.05.14.

43. Pat. 2103396 RF. The method of processing solutions of industrial production of metals of platinum group / V.Nadsonova, Yu.A.Sidenko. 1997.01.29.

44. Pat. 2086685 RF. The method of pyrometallurgical refining of gold and silver-containing waste. 1995.12.14.

45. Pat. 2096508 RF. The method of extraction of silver from materials containing silver chloride, gold impurities and platinum-group metals / S.Loleite et al. 1996.07.05.

46. \u200b\u200bPat. 2086707 RF. The method of extracting noble metals from cyanide solutions / Yu.A. Sididenko et al. 1999.02.22.

47. Pat. 2170277 RF. The method of obtaining silver chloride from industrial-duks containing silver chloride / E.D.Musin, A.I.Karpukhin G.G. Mnisov. 1999.07.15.

48. Pat. 2164255 RF. The method of extracting noble metals from products containing silver chloride, platinum groups / Yu.Sidorenko et al. 1999.02.04.

49. Khudyakov I.F. Metallurgy copper, nickel, concomitant elements and design of workshops / I.F. Khudyakov, S.E. Klyain, N.G.Ageev. M.: Metallurgy. 1993. P. 198-199.

50. Khudyakov I.F. Metallurgy of copper, nickel and cobalt / I.F. Khudyakov, A.I.Tikhonov, V.I.Theev, S.S. Nababenao. M.: Metallurgy. 1977. T.1. C.276-177.

51. Pat. 2152459 RF. Method of electrolytic refining of copper / G.P.Miroevsky K.A. Demidov, I.G. Ermakov et al. 2000.07.10.

52. A.S. 1668437 USSR. The method of processing waste containing non-ferrous metals / S.M. Krichunov, V.G. Blobanov et al. 1989.08.09.

53. Pat. 2119964 RF. The method of extracting noble metals / A.A.ANtonov, A.V. Morozov, K.I. Kryshchenko. 2000.09.12.

54. Pat. 2109088 RF. Multiscount flow electrolyzer for removing metals from solutions of their salts / A.D. Korenevsky, V.A.Dmitriev, K.N. Kryachko. 1996.07.11.

55. Pat. 2095478 RF. Method for extracting gold from waste / V.A. Bogdanovskaya et al. 1996.04.25.

56. Pat. 2132399 RF. Method for processing alloy of platinum group metals / V.I. Bogdanov et al. 1998.04.21.

57. Pat. 2164554 RF. The method of isolating the noble metals from the solution / V.P. Karmannikov. 2000.01.26.

58. Pat. 2093607 RF. The electrolytic method of purification of concentrated solicinal solutions of platinum containing impurities / Z. Hemanman, U. Hadau. 1993.12.17.

59. Pat. 2134307 RF. The method of extracting noble metals from solutions of the LP.P.Zozululy et al. 2000.03.06.

60. Pat. 2119964 RF. The method of extraction of noble metals and installation for its implementation / E.A. Petrov, A.A.Samarov, MG Makarenko. 1997.12.05.

61. Pat. 2027785 RF. The method of extracting noble metals (gold and silver) from solid materials / V.G. Blobanov, V.I. Krayev et al. 1995.05.31.

62. Pat. 2211251 RF. The method of selective extraction of platinum group metals from anodic sludge / V.I.Petric. 2001.09.04.

63. Pat. 2194801 RF. The method of extraction of gold and / or silver from waste / V.M. Boycharev et al. 2001.08.06.

64. Pat. 2176290 RF. The method of electrolytic regeneration of silver silver coating on silver-based / O.G.Gromov, A.P. Kuzmin et al. 2006.08.

65. Pat. 2098193 of the Russian Federation. Installation for the extraction of substances and particles (gold, platinum, silver) from suspensions and solutions / V.S. Jabere. 1995.07.26.

66. Pat. 2176279 RF. The method of recycling secondary gold-containing raw materials into pure gold / L.A.Doronicheva et al. 2001.03.23.

67. Pat. 1809969 RF. The method of extracting platinum IV from salt-sized solutions / Yu.N. Poddayev, etc. 1991.03.04.

68. Pat. 2095443 RF. The method of extracting noble metals from solutions / V.A. Gurov, V.S.Ivanov. 1996.09.03.

69. Pat. 2109076 RF. A method of processing waste containing copper, zinc, silver and gold / G.V. Merevkin, V.V. Denisov. 1996. 02.14.

70. Pat. 2188247 RF. The method for extracting platinum metals from solutions of affinent production / N.I.Timofiev et al. 2001.03.07.

71. Pat. 2147618 RF. The method of purification of noble metals from impurities / L.A. Voropanova. 1998.03.10.

72. Pat. 2165468 RF. The method of extraction of silver from used photoreranges, washing and wastewater / E.A.Petrov et al. 1999.09.28.

73. Pat. 2173724 RF. The method of extracting noble metals from slags / R.S.aleev et al. 1997.11.12.

74. Brockmier K. Induction melting furnaces. M.: Energy, 1972.

75. Farbman S.A. Induction furnaces for melting metals and alloys / S.A. Farbman, I.F. Kolovaev. M.: Metallurgy, 1968.

76. SASSA B.C. Lining induction furnaces and mixers. M.: Energo-Atomizdat, 1983.

77. Sassa B.c. Lining induction furnaces. M.: Metallurgy, 1989.

78. Tsiginov V.A. Melting non-ferrous metals in induction furnaces. M.: Metallurgy, 1974.

79. Bamenko V.V. Electric slip furnaces of non-ferrous metallurgy / V.V. Bamenko, A.V. Donskaya, I.M. Solomakhin. M.: Metallurgy, 1971.

80. Pat. 2164256 RF. The method of processing alloys containing noble and non-ferrous metals / S.G. Yebkin. 1999.05.18.

81. Pat. 2171301 RF. A method for extracting precious metals, in particular silver, from waste / s. Loleit et al. 1999.06.03.

82. Pat. 2110594 RF. The method of extracting noble metals from semi-products / S.V.Digonsky, N.A.Dubyakin, E.D. Kravtsov. 1997.02.21.

83. Pat. 2090633 RF. The method of processing electronic scrap containing noble metals / V.G. Kiraev et al. 1994.12.16.

84. Pat. 2180011 RF. METHOD OF PROCESSING OF LOMA PRODUCTS OF REPUBLICS / Yu.A. Sidido and others 2000.05.03.

85. Pat. 2089635 RF. The method of extraction of silver, gold, platinum and palladium from secondary raw materials containing noble metals / N.A. Yustinchenko et al. 1995.12.14.

86. Pat. 2099434 RF. A method for extracting precious metals from secondary raw materials, mainly from tin-lead solder / S.I.Loleit et al. 1996.07.05.

87. Pat. 2088532 RF. The method of extracting platinum and (or) from spent catalysts based on mineral oxides / A.S. Bely et al. 1993.11.29.

88. Pat. 20883705 RF. The method of extracting noble metals from alumina materials and waste production / Ya.M. Baum, S.S. Jurov, Yu.V. Borisov. 1995.12.13.

89. Pat. 2111791 RF. A method for extracting platinum from exhaust platy-containing catalysts based on aluminum oxide / S.E.Piridonov et al. 1997.06.17.

90. Pat. 2181780 RF. The method of extracting gold from gold-containing polymetallic materials / S.E.Piridonov. 1997.06.17.

91. Pat. 2103395 RF. A method for extracting platinum from spent catalysts /E.P. Bucikhin et al. 1996.09.18.

92. Pat. 2100072 RF. The method of joint extraction of platinum and rhenium from spent platinum-rhenium catalysts / V.F. Blubat, L.N.Adeev. 1996.09.25.

93. Pat. 2116362 RF. The method of extracting precious metals from spent catalysts / R.S.aleev et al. 1997.04.01.

94. Pat. 2124572 RF. The method of removing platinum from deactivated aluminum-platinum catalysts / I.A.Apraxin et al. 1997.12.30.

95. Pat. 2138568 RF. The method of processing spent catalysts containing metals of the platinum group / S.E. Bezheyev et al. 1998.07.13.

96. Pat. 2154686 RF. The method of preparation of spent catalysts, including a carrier containing at least one noble metal, to the subsequent extraction of this metal / E.A. Petrov et al. 1999.02.22.

97. Pat. 2204619 RF. The method of processing aluminoplastic catalysts, mainly containing rhenium / E.A.Shpachev, G.A. Gorev. 2001.01.09.

98. Weisberg J1.A. Regeneration of platinum-palladium regeneration technologies Exhaust catalysts / L.A. Yuisberg, L.P.Zarogatsky // Colored metals. 2003. №12. P.48-51.

99. Agritsky V.A. Pyrometallurgical refining of copper. M.: Metallurgy, 1971.

100. Khudyakov I.F. Metallurgy secondary non-ferrous metals / I.F. Khudyakov, A.P.Doroskevich, S.V. Carelov. M.: Metallurgy, 1987.

101. Smirnov V.I. Production of copper and nickel. M.: Metallurgizdat.1950.

102. Sevryukov N.N. General Metallurgy / N.N.Sevryukov, B.A. Kuzmin, E.V. Chelenishchev. M.: Metallurgy, 1976.

103. Bolchovitinov N.F. Metal studies and thermal processing. M.: State ed. Scientific and technical engineering literature, 1954.

104. Volsky A.I. The theory of metallurgical processes / A.I.Volsky, E.M. Sergievskaya. M.: Metallurgy, 1988.

105. Brief reference book of physico-chemical values. L.: Chemistry, 1974.

106. Shealygin L.M. Impact of blasting conditions for the character of heat mass exchange in a converter bath // Colored metals. 1998. №4. P.27-30

107. Shealygin L.M. The structure of the heat balance, heat generation and te-ploperenos in autogenic metallurgical devices of different types // Colored metals. 2003. №10. P. 17-25.

108. Shealygin L.M. et al. Conditions for supplying a blast in the melts and the development of means of intensifying the blowing regime // Notes of the Mining Institute. 2006. T. 169. p.231-237.

109. Frankel N.Z. Hydraulics. M.: GEI. 1956.

110. Emanuel N.M. Course of chemical kinetics / N.M. Emanuel, D.G. Knorre. M.: Higher School. 1974.

111. Delmon B. Kinetics of heterogeneous reactions. M.: Mir, 1972.

112. Gorlenkov D.V. The method of dissolving copper-nickel anodes containing noble metals / D.V. Gorlenkov, P.A. Pechersky, etc. // Notes of the Mining Institute. T. 169. 2006. P. 108-110.

113. Belov S.F. Prospects for the use of sulfamic acid for the processing of secondary raw materials containing noble and non-ferrous metals / S.F. Belov, T.I.Avayeva, G.D.Sedredina // Non-ferrous metals. №5. 2000.

114. Greyver T.N. The creation of methods for processing complex and nonconformation raw materials containing rare and platinum metals / T.N.Greiver, G.V.Petrov // Colored metals. №12. 2000.

115. Yarosh Yu.B. Development and development of the hydrometallurgical scheme for the extraction of noble metals from the radio electronic scrap / Yu.B. Yarosh, A.V.Fursov, V.V. Sambrasov et al. // Colored metals. №5.2001.

116. Tikhonov I.V. Development of an optimal processing scheme of products containing platinum metals / I.V.Tikhonov, Yu.V.Blagodatin, etc. // Colored metals. №6.2001.

117. Grechko A.V. Barbota pyrometallurgical recycling of waste is different industrial production / A.V.Grechko, V.M. Taretsky, A.D. Wesser // Colored metals. №1.2004.

118. Mikheev A.D. Extraction of silver from electronic scrap / A.D. Mahayev, A.A. Kolmakova, A.I. Grümin, A.A.Colmakov // Colored metals. №5. 2004.

119. Kazantsev S.F. Recycling technogenic waste containing non-ferrous metals / S.F. Kazansev, G.K.Miseiseev et al. // Colored metals. №8. 2005.

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