Scheme of enrichment of tungsten clay ore. Enrichment of tin and tungsten ores and placers. The mining industry deals with solid minerals, from which, with the current level of technology, it is advisable to extract metals or other
Scheelite ores in Russia, and also in some cases abroad, are enriched by flotation. In Russia, the process of flotation of scheelite ores on an industrial scale was carried out before the Second World War at the Tyrny-Auz factory. This factory processes very complex molybdenum-scheelite ores containing a number of calcium minerals (calcite, fluorite, apatite). Calcium minerals, like scheelite, are floated with oleic acid, the depression of calcite and fluorite is produced by mixing in a liquid glass solution without heating (long contact) or with heating, as at the Tyrny-Auz factory. Instead of oleic acid, tall oil fractions are used, as well as acids from vegetable oils (reagents 708, 710, etc.) alone or in a mixture with oleic acid.
A typical scheme of scheelite ore flotation is given in fig. 38. According to this scheme, it is possible to remove calcite and fluorite and obtain concentrates that are conditioned in terms of tungsten trioxide. Ho apatite still remains in such quantity that the phosphorus content in the concentrate is above the standards. Excess phosphorus is removed by dissolving apatite in weak hydrochloric acid. The consumption of acid depends on the content of calcium carbonate in the concentrate and is 0.5-5 g of acid per ton of WO3.
In acid leaching, part of the scheelite, as well as powellite, is dissolved and then precipitated from solution in the form of CaWO4 + CaMoO4 and other impurities. The resulting dirty sediment is then processed according to the method of I.N. Maslenitsky.
Due to the difficulty of obtaining a conditioned tungsten concentrate, many factories abroad produce two products: a rich concentrate and a poor one for hydrometallurgical processing into calcium tungstate according to the method developed in Mekhanobre I.N. Maslenitsky, - leaching with soda in an autoclave under pressure with transfer to a solution in the form of CaWO4, followed by purification of the solution and precipitation of CaWO4. In some cases, with coarsely disseminated scheelite, finishing of flotation concentrates is carried out on tables.
From ores containing a significant amount of CaF2, the extraction of scheelite abroad by flotation has not been mastered. Such ores, for example in Sweden, are enriched on tables. Scheelite entrained with fluorite in the flotation concentrate is then recovered from this concentrate on a table.
At factories in Russia, scheelite ores are enriched by flotation, obtaining conditioned concentrates.
At the Tyrny-Auz plant, ore with a content of 0.2% WO3 is used to produce concentrates with a content of 6о% WO3 with an extraction of 82%. At the Chorukh-Dairon plant, with the same ore in terms of VVO3 content, 72% WO3 is obtained in concentrates with an extraction of 78.4%; at the Koitash plant, with ore with 0.46% WO3 in concentrate, 72.6% WO3 is obtained with a WO3 recovery of 85.2%; at the Lyangar plant in ore 0.124%, in concentrates - 72% with an extraction of 81.3% WO3. Additional separation of poor products is possible by reducing losses in the tailings. In all cases, if sulfides are present in the ore, they are isolated before scheelite flotation.
The consumption of materials and energy is illustrated by the data below, kg/t:
Wolframite (Hübnerite) ores are enriched exclusively by gravity methods. Some ores with uneven and coarse-grained dissemination, such as the Bukuki ore (Transbaikalia), can be pre-enriched in heavy suspensions, separating about 60% of waste rock at a fineness of -26 + 3 MM with a content of no more than 0.03% WO3.
However, with a relatively low productivity of factories (not more than 1000 tons / day), the first stage of enrichment is carried out in jigging machines, usually starting from a particle size of about 10 mm with coarsely disseminated ores. In new modern schemes, in addition to jigging machines and tables, Humphrey screw separators are used, replacing some of the tables with them.
The progressive scheme of enrichment of tungsten ores is given in fig. 39.
Finishing of tungsten concentrates depends on their composition.
Sulfides from concentrates thinner than 2 mm are isolated by flotation gravity: concentrates after mixing with acid and flotation reagents (xanthate, oils) are sent to a concentration table; the resulting CO table concentrate is dried and subjected to magnetic separation. The coarse-grained concentrate is pre-crushed. Sulfides from fine concentrates from slurry tables are isolated by froth flotation.
If there are a lot of sulfides, it is advisable to separate them from the hydrocyclone drain (or classifier) before enrichment on the tables. This will improve the conditions for separating wolframite on the tables and during concentrate finishing operations.
Typically, coarse concentrates prior to finishing contain about 30% WO3 with recovery up to 85%. For illustration in table. 86 shows some data on factories.
During gravitational enrichment of wolframite ores (hubnerite, ferberite) from slimes thinner than 50 microns, the extraction is very low and losses in the slime part are significant (10-15% of the content in the ore).
From sludges by flotation with fatty acids at pH=10, additional WO3 can be recovered into lean products containing 7-15% WO3. These products are suitable for hydrometallurgical processing.
Wolframite (Hübnerite) ores contain a certain amount of non-ferrous, rare and precious metals. Some of them pass during gravitational enrichment into gravitational concentrates and are transferred to finishing tailings. Molybdenum, bismuth-lead, lead-copper-silver, zinc (they contain cadmium, indium) and pyrite concentrates can be isolated by selective flotation from sulfide tailings, as well as from sludge, and the tungsten product can also be additionally isolated.
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In this paper, technologies for the enrichment of scheelite and wolframite are considered.
The technology of enrichment of tungsten ores includes: preliminary concentration, enrichment of crushed products of preliminary concentration to obtain collective (rough) concentrates and their refinement.
Keywords
Scheelite ore, wolframite ore, heavy medium separation, jigging, gravity method, electromagnetic separation, flotation.
1. Introduction 4
2. Preconcentration 5
3. Technology of beneficiation of wolframite ores 6
4. Technology of enrichment of Scheelite ores 9
5. Conclusion 12
References 13
Introduction
Tungsten is a silver-white metal with high hardness and a boiling point of about 5500°C.
The Russian Federation has large explored reserves. Its tungsten ore potential is estimated at 2.6 million tons of tungsten trioxide, in which the proven reserves are 1.7 million tons, or 35% of those in the world.
Fields under development in Primorsky Krai: Vostok-2, OJSC Primorsky GOK (1.503%); Lermontovskoye, AOOT Lermontovskaya GRK (2.462%).
The main tungsten minerals are scheelite, hübnerite and wolframite. Depending on the type of minerals, ores can be divided into two types; scheelite and wolframite (huebnerite).
When processing tungsten-containing ores, gravity, flotation, magnetic, as well as electrostatic, hydrometallurgical and other methods are used.
preliminary concentration.
The cheapest and at the same time highly productive methods of preconcentration are gravitational ones, such as heavy media separation and jigging.
Heavy media separation makes it possible to stabilize the quality of the food entering the main processing cycles, to separate not only the waste product, but also to separate the ore into rich coarsely disseminated and poor finely disseminated ore, often requiring fundamentally different processing schemes, since they differ markedly in material composition. The process is characterized by the highest density separation accuracy compared to other gravity methods, which makes it possible to obtain a high recovery of a valuable component with a minimum concentrate yield. When enriching ore in heavy suspensions, a difference in the densities of the separated pieces of 0.1 g/m3 is sufficient. This method can be successfully applied to coarsely disseminated wolframite and scheelite-quartz ores. The results of studies on the enrichment of tungsten ores from the Pun-les-Vignes (France) and Borralha (Portugal) deposits under industrial conditions showed that the results obtained using enrichment in heavy suspensions are much better than when enriched only on jigging machines - into a heavy fraction recovery was more than 93% of the ore.
Jigging in comparison with heavy-medium enrichment, it requires less capital expenditures, allows enriching the material in a wide range of density and fineness. Large-sized jigging is widely used in the enrichment of large- and medium-disseminated ores that do not require fine grinding. The use of jigging is preferable when enriching carbonate and silicate ores of skarn, vein deposits, while the value of the contrast ratio of ores in terms of gravitational composition should exceed one.
Technology of beneficiation of wolframite ores
The high specific gravity of tungsten minerals and the coarse-grained structure of wolframite ores make it possible to widely use gravity processes in their enrichment. To obtain high technological indicators, it is necessary to combine apparatuses with different separating characteristics in the gravitational scheme, in which each previous operation in relation to the next one is, as it were, preparatory, improving the enrichment of the material. A schematic diagram of the enrichment of wolframite ores is shown in fig. one.
Jigging is used starting from the size at which tailings can be identified. This operation is also used for separating coarsely disseminated tungsten concentrates with subsequent regrinding and enrichment of jigging tailings. The basis for choosing the scheme of jigging and the size of the enriched material are the data obtained by separating the density of the material with a size of 25 mm. If the ores are finely disseminated and preliminary studies show that large-sized enrichment and jigging are unacceptable for them, then the ore is enriched in suspension-carrying flows of small thickness, which include enrichment on screw separators, jet chutes, cone separators, locks, concentration tables. With staged grinding and staged enrichment of ore, the extraction of wolframite into rough concentrates is more complete. Rough wolframite gravity concentrates are brought to standard according to developed schemes using wet and dry enrichment methods.
Rich wolframite concentrates are enriched by electromagnetic separation, while the electromagnetic fraction can be contaminated with iron zinc blende, bismuth minerals and partially arsenic (arsenopyrite, scorodite). To remove them, magnetizing roasting is used, which increases the magnetic susceptibility of iron sulfides, and at the same time, sulfur and arsenic, which are harmful to tungsten concentrates, are removed in the form of gaseous oxides. Wolframite (hubnerite) is additionally extracted from sludge by flotation using fatty acid collectors and the addition of neutral oils. Rough gravitational concentrates are relatively easy to bring to standard using electrical methods of enrichment. Flotation and flotation gravity are carried out with the supply of xanthate and blowing agent in a slightly alkaline or slightly acidic medium. If the concentrates are contaminated with quartz and light minerals, then after flotation they are subjected to recleaning on concentration tables.
Similar information.
IRKUTSK STATE TECHNICAL UNIVERSITY
As a manuscript
Artemova Olesya Stanislavovna
DEVELOPMENT OF A TECHNOLOGY FOR THE EXTRACTION OF TUNGSTEN FROM THE OLD TAILINGS OF THE DZHIDA VMK
Specialty 25.00.13 - Enrichment of minerals
dissertations for the degree of candidate of technical sciences
Irkutsk 2004
The work was carried out at the Irkutsk State Technical University.
Scientific adviser: Doctor of Technical Sciences,
Professor K. V. Fedotov
Official opponents: Doctor of Technical Sciences,
Professor Yu.P. Morozov
Candidate of Technical Sciences A.Ya. Mashovich
Lead organization: St. Petersburg State
Mining Institute (Technical University)
The defense will take place on December 22, 2004 at /O* hours at a meeting of the dissertation council D 212.073.02 of the Irkutsk State Technical University at the address: 664074, Irkutsk, st. Lermontov, 83, room. K-301
Scientific Secretary of the Dissertation Council Professor
GENERAL DESCRIPTION OF WORK
The relevance of the work. Tungsten alloys are widely used in mechanical engineering, mining, metalworking industry, and in the production of electric lighting equipment. The main consumer of tungsten is metallurgy.
Increasing the production of tungsten is possible due to the involvement in the processing of complex in composition, difficult to enrich, poor in content of valuable components and off-balance ores, through the widespread use of gravity enrichment methods.
Involvement in the processing of stale tailings from the Dzhida VMK will solve the urgent problem of the raw material base, increase the production of demanded tungsten concentrate and improve the environmental situation in the Trans-Baikal region.
The purpose of the work: to scientifically substantiate, develop and test rational technological methods and modes of enrichment of stale tungsten-containing tailings of the Dzhida VMK.
Idea of the work: study of the relationship between the structural, material and phase compositions of the stale tailings of the Dzhida VMK with their technological properties, which makes it possible to create a technology for processing technogenic raw materials.
The following tasks were solved in the work: to estimate the distribution of tungsten throughout the space of the main technogenic formation of the Dzhida VMK; to study the material composition of the stale tailings of the Dzhizhinsky VMK; to investigate the contrast of stale tailings in the original size according to the content of W and 8 (II); to investigate the gravitational washability of the stale tailings of the Dzhida VMK in various sizes; determine the feasibility of using magnetic enrichment to improve the quality of crude tungsten-containing concentrates; to optimize the technological scheme for the enrichment of technogenic raw materials from the OTO of the Dzhida VMK; to carry out semi-industrial tests of the developed scheme for extracting W from stale tailings of the FESCO.
Research methods: spectral, optical, optical-geometric, chemical, mineralogical, phase, gravitational and magnetic methods for analyzing the material composition and technological properties of the original mineral raw materials and enrichment products.
The reliability and validity of scientific provisions, conclusions are provided by a representative volume of laboratory research; confirmed by the satisfactory convergence of the calculated and experimentally obtained enrichment results, the correspondence of the results of laboratory and pilot tests.
NATIONAL LIBRARY I Spec glyle!
Scientific novelty:
1. It has been established that technogenic tungsten-containing raw materials of the Dzhida VMK in any size are effectively enriched by the gravitational method.
2. With the help of generalized curves of gravitational dressing, the limiting technological parameters for processing stale tailings of the Dzhida VMK of various sizes by the gravitational method were determined and the conditions for obtaining dump tailings with minimal losses of tungsten were identified.
3. New patterns of separation processes have been established, which determine the gravitational washing of tungsten-containing technogenic raw materials with a particle size of +0.1 mm.
4. For the old tailings of the Dzhida VMK, a reliable and significant correlation was found between the contents of WO3 and S(II).
Practical significance: a technology for the enrichment of stale tailings of the Dzhida VMK has been developed, which ensures the effective extraction of tungsten, which makes it possible to obtain a conditioned tungsten concentrate.
Approbation of the work: the main content of the dissertation work and its individual provisions were reported at the annual scientific and technical conferences of the Irkutsk State Technical University (Irkutsk, 2001-2004), the All-Russian School-Seminar for Young Scientists "Leon Readings - 2004" (Irkutsk , 2004), scientific symposium "Miner's Week - 2001" (Moscow, 2001), All-Russian scientific and practical conference "New technologies in metallurgy, chemistry, enrichment and ecology" (St. Petersburg, 2004 .), Plaksinsky Readings - 2004. In full, the dissertation work was presented at the Department of Mineral Processing and Engineering Ecology at ISTU, 2004 and at the Department of Mineral Processing, SPGGI (TU), 2004.
Publications. On the topic of the dissertation, 8 printed publications have been published.
Structure and scope of work. The dissertation work consists of an introduction, 3 chapters, conclusion, 104 bibliographic sources and contains 139 pages, including 14 figures, 27 tables and 3 appendices.
The author expresses his deep gratitude to the scientific adviser, Doctor of Technical Sciences, prof. K.V. Fedotov for professional and friendly guidance; prof. IS HE. Belkova for valuable advice and useful critical remarks made during the discussion of the dissertation work; G.A. Badenikova - for consulting on the calculation of the technological scheme. The author sincerely thanks the staff of the department for the comprehensive assistance and support provided in the preparation of the dissertation.
The objective prerequisites for the involvement of technogenic formations in the production turnover are:
The inevitability of preserving the natural resource potential. It is ensured by a reduction in the extraction of primary mineral resources and a decrease in the amount of damage caused to the environment;
The need to replace primary resources with secondary ones. Due to the needs of production in material and raw materials, including those industries whose natural resource base is practically exhausted;
The possibility of using industrial waste is ensured by the introduction of scientific and technological progress.
The production of products from technogenic deposits, as a rule, is several times cheaper than from raw materials specially mined for this purpose, and is characterized by a quick return on investment.
Ore beneficiation waste storage facilities are objects of increased environmental hazard due to their negative impact on the air basin, underground and surface waters, and soil cover over vast areas.
Pollution payments are a form of compensation for economic damage from emissions and discharges of pollutants into the environment, as well as for waste disposal on the territory of the Russian Federation.
The Dzhida ore field belongs to the high-temperature deep hydrothermal quartz-wolframite (or quartz-hubnerite) type of deposits, which play a major role in the extraction of tungsten. The main ore mineral is wolframite, whose composition ranges from ferberite to pobnerite with all intermediate members of the series. Scheelite is a less common tungstate.
Ores with wolframite are enriched mainly according to the gravity scheme; usually gravitational methods of wet enrichment are used on jigging machines, hydrocyclones and concentration tables. Magnetic separation is used to obtain conditioned concentrates.
Until 1976, ores at the Dzhida VMK plant were processed according to a two-stage gravity scheme, including heavy-medium enrichment in hydrocyclones, a two-stage concentration of narrowly classified ore materials on three-deck tables of the SK-22 type, regrinding and enrichment of industrial products in a separate cycle. The sludge was enriched according to a separate gravity scheme using domestic and foreign concentration sludge tables.
From 1974 to 1996 tailings of enrichment of only tungsten ores were stored. In 1985-86, ores were processed according to the gravity-flotation technological scheme. Therefore, the tailings of gravity enrichment and the sulphide product of flotation gravity were dumped into the main tailing dump. Since the mid-1980s, due to the increased flow of ore supplied from the Inkursky mine, the proportion of waste from large
classes, up to 1-3 mm. After the shutdown of the Dzhida Mining and Processing Plant in 1996, the settling pond self-destructed due to evaporation and filtration.
In 2000, the “Emergency Discharge Tailing Facility” (HAS) was singled out as an independent object due to its rather significant difference from the main tailing facility in terms of occurrence conditions, the scale of reserves, the quality and degree of preservation of technogenic sands. Another secondary tailing is alluvial technogenic deposits (ATO), which include redeposited flotation tailings of molybdenum ores in the area of the river valley. Modonkul.
The basic standards for payment for waste disposal within the established limits for the Dzhida VMK are 90,620,000 rubles. The annual environmental damage from land degradation due to the placement of stale ore tailings is estimated at 20,990,200 rubles.
Thus, the involvement in the processing of stale tailings of the Dzhida VMK ore enrichment will allow: 1) to solve the problem of the enterprise's raw material base; 2) to increase the output of the demanded "-concentrate" and 3) to improve the ecological situation in the Trans-Baikal region.
The material composition and technological properties of the technogenic mineral formation of the Dzhida VMK
Geological testing of stale tailings of the Dzhida VMK was carried out. When examining a side tailing dump (Emergency Discharge Tailing Facility (HAS)) 13 samples were taken. 5 samples were taken on the area of the ATO deposit. The area of sampling of the main tailing dump (MTF) was 1015 thousand m2 (101.5 ha), 385 partial samples were taken. The mass of the samples taken is 5 tons. All the samples taken were analyzed for the content of "03 and 8 (I).
OTO, CHAT and ATO were statistically compared in terms of the content of "03" using Student's t-test. With a confidence probability of 95%, it was established: 1) the absence of a significant statistical difference in the content of "03" between private samples of side tailings; 2) the average results of testing of the OTO in terms of the content of "03" in 1999 and 2000 refer to the same general population; 3) the average results of testing the main and secondary tailings in terms of the content of "03" significantly differ from each other and the mineral raw materials of all tailings cannot be processed according to the same technology.
The subject of our study is general relativity.
The material composition of the mineral raw materials of the OTO of the Dzhida VMK was established according to the analysis of ordinary and group technological samples, as well as the products of their processing. Random samples were analyzed for the content of "03 and 8(11). Group samples were used for mineralogical, chemical, phase and sieve analyses.
According to the spectral semi-quantitative analysis of a representative analytical sample, the main useful component - " and secondary - Pb, /u, Cu, Au and Content "03 in the form of scheelite
quite stable in all size classes of various sand differences and averages 0.042-0.044%. The content of WO3 in the form of hübnerite is not the same in different size classes. High contents of WO3 in the form of hübnerite are noted in particles of size +1 mm (from 0.067 to 0.145%) and especially in the -0.08+0 mm class (from 0.210 to 0.273%). This feature is typical for light and dark sands and is retained for the averaged sample.
The results of spectral, chemical, mineralogical and phase analyzes confirm that the properties of hubnerite, as the main mineral form \UO3, will determine the technology of enrichment of mineral raw materials by OTO Dzhida VMK.
The granulometric characteristics of raw materials OTO with the distribution of tungsten by size classes is shown in fig. 1.2.
It can be seen that the bulk of the OTO sample material (~58%) has a fineness of -1 + 0.25 mm, 17% each fall into large (-3 + 1 mm) and small (-0.25 + 0.1 mm) classes . The proportion of material with a particle size of -0.1 mm is about 8%, of which half (4.13%) falls on the sludge class -0.044 + 0 mm.
Tungsten is characterized by a slight fluctuation (0.04-0.05%) in the content in size classes from -3 +1 mm to -0.25 + 0.1 mm and a sharp increase (up to 0.38%) in the size class -0 .1+0.044 mm. In the slime class -0.044+0 mm, the tungsten content is reduced to 0.19%. That is, 25.28% of tungsten is concentrated in the -0.1 + 0.044 mm class with an output of this class of about 4% and 37.58% - in the -0.1 + 0 mm class with an output of this class of 8.37%.
As a result of the analysis of data on the impregnation of hubnerite and scheelite in the mineral raw materials OTO of the initial size and crushed to - 0.5 mm (see Table 1).
Table 1 - Distribution of grains and intergrowths of pobnerite and scheelite by size classes of the initial and crushed mineral raw materials _
Size classes, mm Distribution, %
Huebnerite Scheelite
Free grains | Splices grains | Splices
OTO material in original size (- 5 +0 mm)
3+1 36,1 63,9 37,2 62,8
1+0,5 53,6 46,4 56,8 43,2
0,5+0,25 79,2 20,8 79,2 20,8
0,25+0,125 88,1 11,9 90,1 9,9
0,125+0,063 93,6 6,4 93,0 7,0
0,063+0 96,0 4,0 97,0 3,0
Amount 62.8 37.2 64.5 35.5
OTO material ground to - 0.5 +0 mm
0,5+0,25 71,5 28,5 67,1 32,9
0,25+0,125 75,3 24,7 77,9 22,1
0,125+0,063 89,8 10,2 86,1 13,9
0,063+0 90,4 9,6 99,3 6,7
Amount 80.1 19.9 78.5 21.5
It is concluded that it is necessary to classify deslimed mineral raw materials OTO by size of 0.1 mm and separate enrichment of the resulting classes. From the large class, it follows: 1) to separate free grains into a rough concentrate, 2) to subject the tailings containing intergrowths to regrinding, desliming, combining with the deslimed class -0.1 + 0 mm of the original mineral raw materials and gravity enrichment to extract fine grains of scheelite and pobnerite into a middling.
To assess the contrast of mineral raw materials OTO, a technological sample was used, which is a set of 385 individual samples. The results of fractionation of individual samples according to the content of WO3 and sulfide sulfur are shown in Fig.3,4.
0 S OS 0.2 "l M ol O 2 SS * _ " 8
S(kk|Jupytetr"oknsmm"fr**m.% Contain gulfkshoYa
Rice. Fig. 3 Conditional contrast curves of the initial Fig. 4 Conditional contrast curves of the initial
mineral raw materials OTO according to the content N / O) mineral raw materials OTO according to the content 8 (II)
It was found that the contrast ratios for the content of WO3 and S (II) are 0.44 and 0.48, respectively. Taking into account the classification of ores by contrast, the investigated mineral raw materials according to the content of WO3 and S (II) belong to the category of non-contrast ores. Radiometric enrichment is not
suitable for extracting tungsten from small-sized stale tailings of the Dzhida VMK.
The results of the correlation analysis, which revealed a mathematical relationship between the concentrations of \\O3 and S (II) (C3 = 0»0232+0.038C5(u) and r=0.827; the correlation is reliable and reliable), confirm the conclusions about the inexpediency of using radiometric separation.
The results of the analysis of the separation of OTO mineral grains in heavy liquids prepared on the basis of selenium bromide were used to calculate and plot gravity washability curves (Fig. 5), from the form of which, especially the curve, it follows that OTO of Dzhida VMK is suitable for any mineral gravitational enrichment method.
Taking into account the shortcomings in the use of gravitational enrichment curves, especially the curve for determining the metal content in the surfaced fractions with a given yield or recovery, generalized gravity enrichment curves were built (Fig. 6), the results of the analysis of which are given in Table. 2.
Table 2 - Forecast technological indicators of enrichment of different size classes of stale tailings of the Dzhida VMK by the gravity method_
g Grade size, mm Maximum losses \Y with tailings, % Tailings yield, % XV content, %
in the tails in the end
3+1 0,0400 25 82,5 0,207 0,1
3+0,5 0,0400 25 84 0,19 0,18
3+0,25 0,0440 25 90 0,15 0,28
3+0,1 0,0416 25 84,5 0,07 0,175
3+0,044 0,0483 25 87 0,064 0,27
1+0,5 0,04 25 84,5 0,16 0,2
1+0,044 0,0500 25 87 0,038 0,29
0,5+0,25 0,05 25 92,5 0,04 0,45
0,5+0,044 0,0552 25 88 0,025 0,365
0,25+0,1 0,03 25 79 0,0108 0,1
0,25+0,044 0,0633 15 78 0,02 0,3
0,1+0,044 0,193 7 82,5 0,018 1,017
In terms of gravitational washability, classes -0.25+0.044 and -0.1+0.044 mm differ significantly from material of other sizes. The best technological indicators of gravitational enrichment of mineral raw materials are predicted for the size class -0.1+0.044 mm:
The results of electromagnetic fractionation of heavy fractions (HF), gravitational analysis using a universal Sochnev C-5 magnet and magnetic separation of HF showed that the total yield of strongly magnetic and non-magnetic fractions is 21.47% and the losses "in them are 4.5%. Minimum losses "with non-magnetic fraction and the maximum content" in the combined weakly magnetic product is predicted if the separation feed in a strong magnetic field has a particle size of -0.1 + 0 mm.
Rice. 5 Gravity washability curves for stale tailings of the Dzhida VMK
f) class -0.1+0.044 mm
Rice. 6 Generalized curves of gravitational washability of various size classes of mineral raw materials OTO
Development of a technological scheme for the enrichment of stale tailings of the Dzhida VM K
The results of technological testing of various methods of gravitational enrichment of stale tailings of the Dzhida VMK are presented in Table. 3.
Table 3 - Results of testing gravity devices
Comparable technological indicators have been obtained for the extraction of WO3 into a rough concentrate during the enrichment of unclassified stale tailings both with screw separation and centrifugal separation. The minimum losses of WO3 with tailings were found during enrichment in a centrifugal concentrator of the -0.1+0 mm class.
In table. 4 shows the granulometric composition of the crude W-concentrate with a particle size of -0.1+0 mm.
Table 4 - Particle size distribution of crude W-concentrate
Size class, mm Yield of classes, % Content Distribution of AUOz
Absolute Relative, %
1+0,071 13,97 0,11 1,5345 2,046
0,071+0,044 33,64 0,13 4,332 5,831
0,044+0,020 29,26 2,14 62,6164 83,488
0,020+0 23,13 0,28 6,4764 8,635
Total 100.00 0.75 75.0005 100.0
In the concentrate, the main amount of WO3 is in the -0.044+0.020 mm class.
According to the data of mineralogical analysis, in comparison with the source material, the mass fraction of pobnerite (1.7%) and ore sulfide minerals, especially pyrite (16.33%), is higher in the concentrate. The content of rock-forming - 76.9%. The quality of the crude W-concentrate can be improved by successive application of magnetic and centrifugal separation.
The results of testing gravity apparatuses for extracting >UOz from the tailings of the primary gravitational enrichment of mineral raw materials OTO with a particle size of +0.1 mm (Table 5) proved that the most effective apparatus is the KKEL80N concentrator
Table 5 - Results of testing gravity apparatus
Product G,% ßwo>, % rßwo> st ">, %
screw separator
Concentrate 19.25 0.12 2.3345 29.55
Tailings 80.75 0.07 5.5656 70.45
Initial sample 100.00 0.079 7.9001 100.00
wing gateway
Concentrate 15.75 0.17 2.6750 33.90
Tailings 84.25 0.06 5.2880 66.10
Initial sample 100.00 0.08 7.9630 100.00
concentration table
Concentrate 23.73 0.15 3.56 44.50
Tailings 76.27 0.06 4.44 55.50
Initial sample 100.00 0.08 8.00 100.00
centrifugal concentrator KC-MD3
Concentrate 39.25 0.175 6.885 85.00
Tailings 60.75 0.020 1.215 15.00
Initial sample 100.00 0.081 8.100 100.00
When optimizing the technological scheme for the enrichment of mineral raw materials by the OTO of the Dzhida VMK, the following were taken into account: 1) technological schemes for the processing of finely disseminated wolframite ores of domestic and foreign enrichment plants; 2) technical characteristics of the modern equipment used and its dimensions; 3) the possibility of using the same equipment for the simultaneous implementation of two operations, for example, the separation of minerals by size and dehydration; 4) economic costs for hardware design of the technological scheme; 5) the results presented in Chapter 2; 6) GOST requirements for the quality of tungsten concentrates.
During semi-industrial testing of the developed technology (Fig. 7-8 and Table 6), 15 tons of initial mineral raw materials were processed in 24 hours.
The results of a spectral analysis of a representative sample of the obtained concentrate confirm that the W-concentrate of the III magnetic separation is conditioned and corresponds to the grade KVG (T) GOST 213-73.
Fig.8 The results of technological testing of the scheme for finishing rough concentrates and middlings from stale tailings of the Dzhida VMK
Table 6 - Results of testing the technological scheme
Product u
Conditioning concentrate 0.14 62.700 8.778 49.875
Dump tailings 99.86 0.088 8.822 50.125
Source ore 100.00 0.176 17.600 100.000
CONCLUSION
The paper gives a solution to an urgent scientific and production problem: scientifically substantiated, developed and, to a certain extent, implemented effective technological methods for extracting tungsten from the stale tailings of the Dzhida VMK ore concentration.
The main results of the research, development and their practical implementation are as follows
The main useful component is tungsten, according to the content of which stale tailings are a non-contrast ore, it is represented mainly by hubnerite, which determines the technological properties of technogenic raw materials. Tungsten is unevenly distributed over size classes and its main amount is concentrated in size
It has been proved that the only effective method of enrichment of W-containing stale tailings of the Dzhida VMK is gravity. Based on the analysis of the generalized curves of the gravitational concentration of stale W-containing tailings, it has been established that dump tailings with minimal losses of tungsten are a hallmark of the enrichment of technogenic raw materials with a particle size of -0.1 + Omm. New patterns of separation processes have been established that determine the technological parameters of gravity enrichment of stale tailings of the Dzhida VMK with a fineness of +0.1 mm.
It has been proved that among the gravity apparatuses used in the mining industry in the enrichment of W-containing ores, for the maximum extraction of tungsten from technogenic raw materials of the Dzhida VMK into rough W-concentrates, a screw separator and a KKEb80N tailings of primary enrichment of technogenic W-containing raw materials in size - 0.1 mm.
3. The optimized technological scheme for the extraction of tungsten from the stale tailings of the Dzhida VMK ore concentration made it possible to obtain a conditioned W-concentrate, solve the problem of depletion of the mineral resources of the Dzhida VMK and reduce the negative impact of the enterprise's production activities on the environment.
Preferred use of gravity equipment. During semi-industrial tests of the developed technology for extracting tungsten from the stale tailings of the Dzhida VMK, a conditioned "-concentrate with a content of" 03 62.7% was obtained with an extraction of 49.9%. The payback period for the enrichment plant for processing stale tailings of the Dzhida VMK for the purpose of extracting tungsten was 0.55 years.
The main provisions of the dissertation work are published in the following works:
1. Fedotov K.V., Artemova O.S., Polinskina I.V. Assessment of the possibility of processing stale tailings of the Dzhida VMK, Ore dressing: Sat. scientific works. - Irkutsk: Publishing house of ISTU, 2002. - 204 p., S. 74-78.
2. Fedotov K.V., Senchenko A.E., Artemova O.S., Polinkina I.V. The use of a centrifugal separator with continuous discharge of concentrate for the extraction of tungsten and gold from the tailings of the Dzhida VMK, Environmental problems and new technologies for the complex processing of mineral raw materials: Proceedings of the International Conference "Plaksinsky Readings - 2002". - M.: P99, Publishing House of the PCC "Altex", 2002 - 130 p., P. 96-97.
3. Zelinskaya E.V., Artemova O.S. The possibility of adjusting the selectivity of the action of the collector during the flotation of tungsten-containing ores from stale tailings, Directed changes in the physico-chemical properties of minerals in the processes of mineral processing (Plaksin Readings), materials of the international meeting. - M.: Alteks, 2003. -145 s, p.67-68.
4. Fedotov K.V., Artemova O.S. Problems of processing stale tungsten-containing products Modern methods of processing mineral raw materials: Conference materials. Irkutsk: Irk. State. Those. University, 2004 - 86 p.
5. Artemova O. S., Gaiduk A. A. Extraction of tungsten from stale tailings of the Dzhida tungsten-molybdenum plant. Prospects for the development of technology, ecology and automation of chemical, food and metallurgical industries: Proceedings of the scientific and practical conference. - Irkutsk: Publishing house of ISTU. - 2004 - 100 p.
6. Artemova O.S. Assessment of the uneven distribution of tungsten in the Dzhida tailing. Modern methods for assessing the technological properties of mineral raw materials of precious metals and diamonds and progressive technologies for their processing (Plaksin Readings): Proceedings of the international meeting. Irkutsk, September 13-17, 2004 - M.: Alteks, 2004. - 232 p.
7. Artemova O.S., Fedotov K.V., Belkova O.N. Prospects for the use of the technogenic deposit of the Dzhida VMK. All-Russian scientific and practical conference "New technologies in metallurgy, chemistry, enrichment and ecology", St. Petersburg, 2004
Signed for printing 12. H 2004. Format 60x84 1/16. Printing paper. Offset printing. Conv. oven l. Uch.-ed.l. 125. Circulation 400 copies. Law 460.
ID No. 06506 dated December 26, 2001 Irkutsk State Technical University 664074, Irkutsk, st. Lermontova, 83
RNB Russian Fund
1. SIGNIFICANCE OF MAN-MADE MINERAL RAW MATERIALS
1.1. Mineral resources of the ore industry in the Russian Federation and the tungsten sub-industry
1.2. Technogenic mineral formations. Classification. The need to use
1.3. Technogenic mineral formation of the Dzhida VMK
1.4. Goals and objectives of the study. Research methods. Provisions for defense
2. INVESTIGATION OF THE MATERIAL COMPOSITION AND TECHNOLOGICAL PROPERTIES OF OLD TAILINGS OF THE DZHIDA VMK
2.1. Geological sampling and evaluation of tungsten distribution
2.2. The material composition of mineral raw materials
2.3. Technological properties of mineral raw materials
2.3.1. Grading
2.3.2. Study of the possibility of radiometric separation of mineral raw materials in the initial size
2.3.3. Gravity Analysis
2.3.4. Magnetic analysis
3. DEVELOPMENT OF A TECHNOLOGICAL SCHEME FOR THE EXTRACTION OF TUNGSTEN FROM THE OLD TAILINGS OF THE DZHIDA VMK
3.1. Technological testing of different gravity devices during the enrichment of stale tailings of various sizes
3.2. Optimization of the GR processing scheme
3.3. Semi-industrial testing of the developed technological scheme for the enrichment of general relativity and industrial plant
Introduction Dissertation in earth sciences, on the topic "Development of technology for extracting tungsten from the stale tailings of the Dzhida VMK"
Mineral enrichment sciences are primarily aimed at developing the theoretical foundations of mineral separation processes and creating enrichment apparatuses, at revealing the relationship between the distribution patterns of components and separation conditions in enrichment products in order to increase the selectivity and speed of separation, its efficiency and economy, and environmental safety.
Despite significant mineral reserves and a reduction in resource consumption in recent years, the depletion of mineral resources is one of the most important problems in Russia. Weak use of resource-saving technologies contributes to large losses of minerals during the extraction and enrichment of raw materials.
An analysis of the development of equipment and technology for mineral processing over the past 10-15 years indicates significant achievements of domestic fundamental science in the field of understanding the main phenomena and patterns in the separation of mineral complexes, which makes it possible to create highly efficient processes and technologies for the primary processing of ores of complex material composition and, as consequently, to provide the metallurgical industry with the necessary range and quality of concentrates. At the same time, in our country, in comparison with developed foreign countries, there is still a significant lag in the development of the machine-building base for the production of main and auxiliary enrichment equipment, in its quality, metal consumption, energy intensity and wear resistance.
In addition, due to the departmental affiliation of mining and processing enterprises, complex raw materials were processed only taking into account the necessary needs of the industry for a particular metal, which led to the irrational use of natural mineral resources and an increase in the cost of waste storage. Currently, more than 12 billion tons of waste have been accumulated, the content of valuable components in which in some cases exceeds their content in natural deposits.
In addition to the above negative trends, starting from the 90s, the environmental situation at mining and processing enterprises has sharply worsened (in a number of regions threatening the existence of not only biota, but also humans), there has been a progressive decline in the extraction of non-ferrous and ferrous metal ores, mining and chemical raw materials, deterioration in the quality of processed ores and, as a result, the involvement in processing of refractory ores of complex material composition, characterized by a low content of valuable components, fine dissemination and similar technological properties of minerals. Thus, over the past 20 years, the content of non-ferrous metals in ores has decreased by 1.3-1.5 times, iron by 1.25 times, gold by 1.2 times, the share of refractory ores and coal has increased from 15% to 40% of the total mass of raw materials supplied for enrichment.
Human impact on the natural environment in the process of economic activity is now becoming global. In terms of the scale of extracted and transported rocks, the transformation of the relief, the impact on the redistribution and dynamics of surface and groundwater, the activation of geochemical transport, etc. this activity is comparable to geological processes.
The unprecedented scale of recoverable mineral resources leads to their rapid depletion, the accumulation of a large amount of waste on the Earth's surface, in the atmosphere and hydrosphere, the gradual degradation of natural landscapes, the reduction of biodiversity, the decrease in the natural potential of territories and their life-supporting functions.
Waste storage facilities for ore processing are objects of increased environmental hazard due to their negative impact on the air basin, underground and surface waters, and soil cover over vast areas. Along with this, tailings are poorly explored man-made deposits, the use of which will make it possible to obtain additional sources of ore and mineral raw materials with a significant reduction in the scale of disturbance of the geological environment in the region.
The production of products from technogenic deposits, as a rule, is several times cheaper than from raw materials specially mined for this purpose, and is characterized by a quick return on investment. However, the complex chemical, mineralogical and granulometric composition of tailings, as well as a wide range of minerals contained in them (from the main and associated components to the simplest building materials) make it difficult to calculate the total economic effect of their processing and determine an individual approach to assessing each tailing.
Consequently, at the moment a number of insoluble contradictions have emerged between the change in the nature of the mineral resource base, i.e. the need to involve in the processing of refractory ores and man-made deposits, the environmentally aggravated situation in the mining regions and the state of technology, technology and organization of the primary processing of mineral raw materials.
The issues of using wastes from the enrichment of polymetallic, gold-bearing and rare metals have both economic and environmental aspects.
V.A. Chanturia, V.Z. Kozin, V.M. Avdokhin, S.B. Leonov, JI.A. Barsky, A.A. Abramov, V.I. Karmazin, S.I. Mitrofanov and others.
An important part of the overall strategy of the mining industry, incl. tungsten, is the growth in the use of ore processing waste as additional sources of ore and mineral raw materials, with a significant reduction in the extent of disturbance of the geological environment in the region and the negative impact on all components of the environment.
In the field of using ore processing waste, the most important is a detailed mineralogical and technological study of each specific, individual technogenic deposit, the results of which will allow the development of an effective and environmentally friendly technology for the industrial development of an additional source of ore and mineral raw materials.
The problems considered in the dissertation work were solved in accordance with the scientific direction of the Department of Mineral Processing and Engineering Ecology of the Irkutsk State Technical University on the topic “Fundamental and technological research in the field of processing of mineral and technogenic raw materials for the purpose of its integrated use, taking into account environmental problems in complex industrial systems ” and the film theme No. 118 “Research on the washability of stale tailings of the Dzhida VMK”.
The purpose of the work is to scientifically substantiate, develop and test rational technological methods for the enrichment of stale tungsten-containing tailings of the Dzhida VMK.
The following tasks were solved in the work:
Assess the distribution of tungsten throughout the space of the main technogenic formation of the Dzhida VMK;
To study the material composition of the stale tailings of the Dzhizhinsky VMK;
Investigate the contrast of stale tailings in the original size by the content of W and S (II); to investigate the gravitational washability of the stale tailings of the Dzhida VMK in various sizes;
Determine the feasibility of using magnetic enrichment to improve the quality of crude tungsten-containing concentrates;
Optimize the technological scheme for the enrichment of technogenic raw materials from the OTO of the Dzhida VMK; to conduct semi-industrial tests of the developed scheme for extracting W from stale tailings of the FESCO;
To develop a scheme of a chain of apparatus for the industrial processing of stale tailings of the Dzhida VMK.
To perform the research, a representative technological sample of stale tailings of the Dzhida VMK was used.
When solving the formulated problems, the following research methods were used: spectral, optical, chemical, mineralogical, phase, gravitational and magnetic methods for analyzing the material composition and technological properties of the initial mineral raw materials and enrichment products.
The following main scientific provisions are submitted for defense: Regularities of distribution of the initial technogenic mineral raw materials and tungsten by size classes are established. The necessity of primary (preliminary) classification by size 3 mm is proved.
Quantitative characteristics of stale tailings of ore-dressing of ores of the Dzhida VMK have been established in terms of the content of WO3 and sulfide sulfur. It is proved that the original mineral raw materials belong to the category of non-contrast ores. A significant and reliable correlation between the contents of WO3 and S (II) was revealed.
Quantitative patterns of gravitational enrichment of stale tailings of the Dzhida VMK have been established. It has been proven that for the source material of any size, an effective method for extracting W is gravity enrichment. The predictive technological indicators of gravitational enrichment of the initial mineral raw materials in various sizes are determined.
Quantitative regularities in the distribution of stale tailings of the Dzhida VMK ore concentration by fractions of different specific magnetic susceptibility have been established. The successive use of magnetic and centrifugal separation has been proven to improve the quality of crude W-containing products. Technological modes of magnetic separation have been optimized.
Conclusion Dissertation on the topic "Enrichment of minerals", Artemova, Olesya Stanislavovna
The main results of the research, development and their practical implementation are as follows:
1. An analysis of the current situation in the Russian Federation with the mineral resources of the ore industry, in particular, the tungsten industry, was carried out. On the example of the Dzhida VMK, it is shown that the problem of involving in the processing of stale ore tailings is relevant, having technological, economic and environmental significance.
2. The material composition and technological properties of the main W-bearing technogenic formation of the Dzhida VMK have been established.
The main useful component is tungsten, according to the content of which stale tailings are a non-contrast ore, it is represented mainly by hubnerite, which determines the technological properties of technogenic raw materials. Tungsten is unevenly distributed over size classes and its main amount is concentrated in size -0.5 + 0.1 and -0.1 + 0.02 mm.
It has been proved that the only effective method of enrichment of W-containing stale tailings of the Dzhida VMK is gravity. Based on the analysis of the generalized curves of the gravitational concentration of stale W-containing tailings, it has been established that dump tailings with minimal losses of tungsten are a hallmark of the enrichment of technogenic raw materials with a particle size of -0.1 + 0 mm. New patterns of separation processes have been established that determine the technological parameters of gravity enrichment of stale tailings of the Dzhida VMK with a fineness of +0.1 mm.
It has been proved that among the gravity devices used in the mining industry in the enrichment of W-containing ores, a screw separator and a KNELSON centrifugal concentrator are suitable for maximum extraction of tungsten from technogenic raw materials of the Dzhida VMK into rough W-concentrates. The effectiveness of the use of the KNELSON concentrator has also been confirmed for the additional extraction of tungsten from the tailings of the primary enrichment of technogenic W-containing raw materials with a particle size of 0.1 mm.
3. The optimized technological scheme for the extraction of tungsten from the stale tailings of the Dzhida VMK ore enrichment made it possible to obtain a conditioned W-concentrate, solve the problem of depletion of the mineral resources of the Dzhida VMK and reduce the negative impact of the enterprise's production activities on the environment.
The essential features of the developed technology for extracting tungsten from the stale tailings of the Dzhida VMK are:
Narrow classification by feed size of primary processing operations;
Preferred use of gravity equipment.
During semi-industrial testing of the developed technology for extracting tungsten from the stale tailings of the Dzhida VMK, a conditioned W-concentrate with a WO3 content of 62.7% was obtained with an extraction of 49.9%. The payback period for the enrichment plant for processing stale tailings of the Dzhida VMK for the purpose of extracting tungsten was 0.55 years.
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Cassiterite SnO 2- the main industrial mineral of tin, which is present in tin-bearing placers and bedrock ores. The content of tin in it is 78.8%. Cassiterite has a density of 6900…7100 kg/t and a hardness of 6…7. The main impurities in cassiterite are iron, tantalum, niobium, as well as titanium, manganese, pigs, silicon, tungsten, etc. The physicochemical properties of cassiterite, for example, magnetic susceptibility, and its flotation activity depend on these impurities.
Stannin Cu 2 S FeS SnS 4- tin sulfide mineral, although it is the most common mineral after cassiterite, has no industrial value, firstly, because it has a low tin content (27 ... 29.5%), and secondly, the presence of copper and iron sulfides in it complicates the metallurgical processing of concentrates and, thirdly, the proximity of the flotation properties of the frame to sulfides makes it difficult to separate them during flotation. The composition of tin concentrates obtained at concentrating plants is different. Gravity concentrates containing as little as 60% tin are released from rich tin placers, and sludge concentrates obtained by both gravity and flotation methods can contain from 15 to 5% tin.
Tin-bearing deposits are divided into placer and primary. Alluvial tin deposits are the main source of world tin mining. About 75% of the world's tin reserves are concentrated in placers. Indigenous tin deposits have a complex material composition, depending on which they are divided into quartz-cassiterite, sulfide-quartz-cassiterite and sulfide-cassiterite.
Quartz-cassiterite ores are usually complex tin-tungsten. Cassiterite in these ores is represented by coarse, medium and finely disseminated crystals in quartz (from 0.1 to 1 mm or more). In addition to quartz and cassiterite, these ores usually contain feldspar, tourmaline, micas, wolframite or scheelite, and sulfides. The sulfide-cassiterite ores are dominated by sulfides - pyrite, pyrrhotite, arsenopyrite, galena, sphalerite and stanin. It also contains iron minerals, chlorite and tourmaline.
Tin placers and ores are enriched mainly by gravity methods using jigging machines, concentration tables, screw separators and locks. Placers are usually much easier to be enriched by gravity methods than ores of primary deposits, because. they do not require expensive crushing and grinding processes. Fine-tuning of rough gravity concentrates is carried out by magnetic, electrical and other methods.
Enrichment at locks is used when the grain size of cassiterite is more than 0.2 mm, because smaller grains are poorly caught on locks and their extraction does not exceed 50 ... 60%. More efficient devices are jigging machines, which are installed for primary enrichment and allow you to extract up to 90% of cassiterite. Fine-tuning of rough concentrates is carried out on concentration tables (Fig. 217).
Fig. 217. Scheme of enrichment of tin placers
The primary enrichment of placers is also carried out on dredges, including sea dredges, where drum screens with holes of 6–25 mm in size are installed for sand washing, depending on the distribution of cassiterite by size class and sand washability. To enrich the undersize product of screens, jigging machines of various designs are used, usually with an artificial bed. Gateways are also installed. Primary concentrates are subjected to cleaning operations on jigging machines. Finishing, as a rule, is carried out at coastal finishing stations. Extraction of cassiterite from placers is usually 90…95%.
Enrichment of primary tin ores, which are distinguished by the complexity of the material composition and uneven dissemination of cassiterite, is carried out according to more complex multi-stage schemes using not only gravity methods, but also flotation gravity, flotation, and magnetic separation.
When preparing tin ores for enrichment, it is necessary to take into account the ability of cassiterite to sludge due to its size. More than 70% of the loss of tin during enrichment is accounted for by sludged cassiterite, which is carried away with drains from gravity apparatuses. Therefore, the grinding of tin ores is carried out in rod mills, which operate in a closed cycle with screens. At some factories, enrichment in heavy suspensions is used at the head of the process, which makes it possible to separate up to 30 ... 35% of host rock minerals into dump tailings, reduce grinding costs and increase tin recovery.
To isolate coarse-grained cosmiterite in the head of the process, jigging is used with a feed size of 2…3 to 15…20 mm. Sometimes, instead of jigging machines, with a material size of minus 3 + 0.1 mm, screw separators are installed, and when enriching a material with a size of 2 ... 0.1 mm, concentration tables are used.
For ores with uneven dissemination of cassiterite, multi-stage schemes are used with sequential regrinding of not only tailings, but also poor concentrates and middlings. In tin ore, which is enriched according to the scheme shown in Fig. 218, cassiterite has a particle size of 0.01 to 3 mm.
Rice. 218. Scheme of gravitational enrichment of primary tin ores
The ore also contains iron oxides, sulfides (arsenopyrite, chalcopyrite, pyrite, stanin, galena), wolframite. The nonmetallic part is represented by quartz, tourmaline, chlorite, sericite, and fluorite.
The first stage of enrichment is carried out in jigging machines with an ore size of 90% minus 10 mm with the release of coarse tin concentrate. Then, after regrinding the tailings of the first stage of enrichment and hydraulic classification according to equal fall, enrichment is carried out on concentration tables. The tin concentrate obtained according to this scheme contains 19 ... 20% of tin with an extraction of 70 ... 85% and is sent for finishing.
When finishing, sulfide minerals, minerals of host rocks, are removed from coarse tin concentrates, which makes it possible to increase the tin content to the standard.
Coarsely disseminated sulfide minerals with a particle size of 2…4 mm are removed by flotation gravity on concentration tables, before which the concentrates are treated with sulfuric acid (1.2…1.5 kg/t), xanthate (0.5 kg/t) and kerosene (1…2 kg/t). t).
Cassiterite is recovered from gravity concentration sludge by flotation using selective collectors and depressants. For ores of complex mineral composition containing significant amounts of tourmaline, iron hydroxides, the use of fatty acid collectors makes it possible to obtain poor tin concentrates containing no more than 2–3% tin. Therefore, when flotation of cassiterite, such selective collectors as Asparal-F or aerosol-22 (succinamates), phosphonic acids and reagent IM-50 (alkylhydroxamic acids and their salts) are used. Water glass and oxalic acid are used to depress the minerals of the host rocks.
Before flotation of cassiterite, material with a particle size of minus 10…15 µm is removed from the sludge, then sulfides are flotation, from the tails of which at pH 5 when oxalic acid, liquid glass and Asparal-F reagent (140…150 g/t) are fed into as a collector, cassiterite is floated (Fig. 219). The resulting flotation concentrate contains up to 12% tin when extracting up to 70...75% tin from the operation.
Sometimes, Bartles-Moseley orbital locks and Bartles-Crosbelt concentrators are used to extract cassiterite from sludge. The rough concentrates obtained on these devices, containing 1 ... 2.5% of tin, are sent for finishing to slurry concentration tables with the production of commercial slurry tin concentrates.
Tungsten in ores it is represented by a wider range of minerals of industrial importance than tin. Of the 22 tungsten minerals currently known, four are the main ones: wolframite (Fe,Mn)WO 4(density 6700 ... 7500 kg / m 3), hubnerite MnWO 4(density 7100 kg / m 3), ferberite FeWO 4(density 7500 kg / m 3) and scheelite CaWO 4(density 5800 ... 6200 kg / m 3). In addition to these minerals, molybdoscheelite, which is scheelite and an isomorphic admixture of molybdenum (6...16%), is of practical importance. Wolframite, hübnerite and ferberite are weakly magnetic minerals; they contain magnesium, calcium, tantalum and niobium as impurities. Wolframite is often found in ores along with cassiterite, molybdenite, and sulfide minerals.
The industrial types of tungsten-containing ores are veined quartz-wolframite and quartz-cassiterite-wolframite, stockwork, skarn and alluvial. In deposits vein type contain wolframite, hubnerite and scheelite, as well as molybdenum minerals, pyrite, chalcopyrite, tin, arsenic, bismuth and gold minerals. AT stockwork In deposits, the content of tungsten is 5 ... 10 times less than in vein deposits, but they have large reserves. AT skarn ores, along with tungsten, represented mainly by scheelite, contain molybdenum and tin. Alluvial tungsten deposits have small reserves, but they play a significant role in the extraction of tungsten. The industrial content of tungsten trioxide in placers (0.03 ... 0.1%) is much lower than in primary ores, but their development is much simpler and economically more profitable. These placers, along with wolframite and scheelite, also contain cassiterite.
The quality of tungsten concentrates depends on the material composition of the enriched ore and the requirements that apply to them when used in various industries. So for the production of ferrotungsten, the concentrate must contain at least 63% WO3, wolframite-huebnerite concentrate for the production of hard alloys must contain at least 60% WO3. Scheelite concentrates typically contain 55% WO3. The main harmful impurities in tungsten concentrates are silica, phosphorus, sulfur, arsenic, tin, copper, lead, antimony and bismuth.
Tungsten placers and ores are enriched, like tin ones, in two stages - primary gravitational enrichment and refinement of rough concentrates by various methods. With a low content of tungsten trioxide in the ore (0.1 ... 0.8%) and high requirements for the quality of concentrates, the total degree of enrichment is from 300 to 600. This degree of enrichment can only be achieved by combining various methods, from gravity to flotation.
In addition, wolframite placers and primary ores usually contain other heavy minerals (cassiterite, tantalite-columbite, magnetite, sulfides), therefore, during primary gravity enrichment, a collective concentrate containing from 5 to 20% WO 3 is released. When finishing these collective concentrates, standard monomineral concentrates are obtained, for which flotation gravity and flotation of sulfides, magnetic separation of magnetite and wolframite are used. It is also possible to use electrical separation, enrichment on concentration tables, and even flotation of minerals from displacement rocks.
The high density of tungsten minerals makes it possible to effectively use gravity enrichment methods for their extraction: in heavy suspensions, on jigging machines, concentration tables, screw and jet separators. In enrichment and especially in the refinement of collective gravitational concentrates, sagnite separation is widely used. Wolframite has magnetic properties and therefore separates in a strong magnetic field, for example, from non-magnetic cassiterite.
The original tungsten ore, as well as tin ore, is crushed to a particle size of minus 12 + 6 mm and enriched with jigging, where coarsely disseminated wolframite and part of the tailings with a tailings content of tungsten trioxide are released. After jigging, the ore is fed to rod mills for grinding, in which it is crushed to a fineness of minus 2+ 0.5 mm. To avoid excessive sludge formation, grinding is carried out in two stages. After crushing, the ore is subjected to hydraulic classification with the release of sludge and the enrichment of sand fractions on concentration tables. The middlings and tailings received on the tables are crushed and sent to the concentration tables. The tailings are also subsequently crushed and enriched on concentration tables. The enrichment practice shows that the extraction of wolframite, hübnerite and ferberite by gravity methods reaches 85%, while scheelite, inclined to sludge, is extracted by gravity methods only by 55 ... 70%.
When enriching finely disseminated wolframite ores containing only 0.05 ... 0.1% of tungsten trioxide, flotation is used.
Flotation is especially widely used to extract scheelite from skarn ores, which contain calcite, dolomite, fluorite and barite, floated by the same collectors as scheelite.
Collectors in the flotation of scheelite ores are fatty acids of the oleic type, which is used at a temperature of at least 18 ... 20 ° C in the form of an emulsion prepared in soft water. Often, oleic acid is saponified in a hot solution of soda ash at a ratio of 1:2 before being fed into the process. Instead of oleic acid, tall oil, naphthenic acids, and the like are also used.
It is very difficult to separate scheelite from alkaline earth minerals containing calcium, barium and iron oxides by flotation. Scheelite, fluorite, apatite and calcite contain calcium cations in the crystal lattice, which provide chemical sorption of the fatty acid collector. Therefore, selective flotation of these minerals from scheelite is possible within narrow pH ranges using depressants such as liquid glass, sodium silicofluoride, soda, sulfuric and hydrofluoric acid.
The depressing effect of liquid glass during the flotation of calcium-containing minerals with oleic acid consists in the desorption of calcium soaps formed on the surface of the minerals. At the same time, the floatability of scheelite does not change, while the floatability of other calcium-containing minerals deteriorates sharply. Increasing the temperature to 80...85°C reduces the contact time of the pulp with a solution of liquid glass from 16 hours to 30...60 minutes. Liquid glass consumption is about 0.7 kg/t. The process of selective scheelite flotation, shown in Fig. 220, using the steaming process with liquid glass, is called the Petrov method.
Rice. 220. Scheme of scheelite flotation from tungsten-molybdenum ores using
fine-tuning according to the Petrov method
The concentrate of the main scheelite flotation, which is carried out at a temperature of 20°C in the presence of oleic acid, contains 4...6% tungsten trioxide and 38...45% calcium oxide in the form of calcite, fluorite and apatite. The concentrate is thickened to 50-60% solid before steaming. Steaming is carried out sequentially in two vats in a 3% solution of liquid glass at a temperature of 80 ... 85 ° C for 30 ... 60 minutes. After steaming, cleaning operations are carried out at a temperature of 20 ... 25 ° C. The resulting scheelite concentrate may contain up to 63...66% of tungsten trioxide with its recovery of 82...83%.
Tungsten is the most refractory metal with a melting point of 3380°C. And this determines its scope. It is also impossible to build electronics without tungsten, even the filament in a light bulb is tungsten.
And, of course, the properties of the metal determine the difficulties in obtaining it ...
First, you need to find the ore. These are just two minerals - scheelite (calcium tungstate CaWO 4) and wolframite (iron and manganese tungstate - FeWO 4 or MnWO 4). The latter has been known since the 16th century under the name "wolf foam" - "Spuma lupi" in Latin, or "Wolf Rahm" in German. This mineral accompanies tin ores and interferes with the smelting of tin, converting it into slag. Therefore, it is possible to find it already in antiquity. Rich tungsten ores usually contain 0.2 - 2% tungsten. In reality, tungsten was discovered in 1781.
However, finding this is the simplest thing in tungsten mining.
Next - the ore needs to be enriched. There are a bunch of methods and they are all quite complex. First, of course. Then - magnetic separation (if we have wolframite with iron tungstate). Next is gravity separation, because the metal is very heavy and the ore can be washed, much like when mining gold. Now they still use electrostatic separation, but it is unlikely that the method will be useful to a hitman.
So, we have separated the ore from the waste rock. If we have scheelite (CaWO 4), then the next step can be skipped, and if wolframite, then we need to turn it into scheelite. To do this, tungsten is extracted with a soda solution under pressure and at elevated temperature (the process takes place in an autoclave), followed by neutralization and precipitation in the form of artificial scheelite, i.e. calcium tungstate.
It is also possible to sinter wolframite with an excess of soda, then we get not calcium tungstate, but sodium, which is not so significant for our purposes (4FeWO 4 + 4Na 2 CO 3 + O 2 = 4Na 2 WO 4 + 2Fe 2 O 3 + 4CO 2).
The next two steps are water leaching of CaWO 4 -> H 2 WO 4 and hot acid decomposition.
You can take different acids - hydrochloric (Na 2 WO 4 + 2HCl \u003d H 2 WO 4 + 2NaCl) or nitric.
As a result, tungsten acid is isolated. The latter is calcined or dissolved in an aqueous solution of NH 3, from which paratungstate is crystallized by evaporation.
As a result, it is possible to obtain the main raw material for the production of tungsten - WO 3 trioxide with good purity.
Of course, there is also a method for obtaining WO 3 using chlorides, when a tungsten concentrate is treated with chlorine at an elevated temperature, but this method will not be simple for a hitman.
Tungsten oxides can be used in metallurgy as an alloying additive.
So, we have tungsten trioxide and one stage remains - reduction to metal.
There are two methods here - hydrogen reduction and carbon reduction. In the second case, coal and the impurities it always contains react with tungsten to form carbides and other compounds. Therefore, tungsten comes out “dirty”, brittle, and for electronics it is very desirable clean, because having only 0.1% iron, tungsten becomes brittle and it is impossible to pull out the thinnest wire for filaments from it.
The technical process with coal has another drawback - a high temperature: 1300 - 1400 ° C.
However, production with hydrogen reduction is also not a gift.
The reduction process takes place in special tube furnaces, heated in such a way that, as it moves along the pipe, the “boat” with WO3 passes through several temperature zones. A stream of dry hydrogen flows towards it. Recovery occurs both in "cold" (450...600°C) and in "hot" (750...1100°C) zones; in the "cold" - to the lowest oxide WO 2, then - to the elemental metal. Depending on the temperature and duration of the reaction in the "hot" zone, the purity and size of the grains of powdered tungsten released on the walls of the "boat" change.
So, we got pure metal tungsten in the form of the smallest powder.
But this is not yet an ingot of metal from which something can be made. The metal is obtained by powder metallurgy. That is, it is first pressed, sintered in a hydrogen atmosphere at a temperature of 1200-1300 ° C, then an electric current is passed through it. The metal is heated to 3000 °C, and sintering into a monolithic material occurs.
However, we rather need not ingots or even rods, but thin tungsten wire.
As you understand, here again, not everything is so simple.
Wire drawing is carried out at a temperature of 1000°C at the beginning of the process and 400-600°C at the end. In this case, not only the wire is heated, but also the die. Heating is carried out by a gas burner flame or an electric heater.
At the same time, after drawing, the tungsten wire is coated with graphite grease. The surface of the wire must be cleaned. Cleaning is carried out by annealing, chemical or electrolytic etching, electrolytic polishing.
As you can see, the task of obtaining a simple tungsten filament is not as simple as it seems. And here only the main methods are described, for sure there are a lot of pitfalls.
And, of course, even now tungsten is an expensive metal. Now one kilogram of tungsten costs more than $50, the same molybdenum is almost two times cheaper.
Actually, there are several uses for tungsten.
Of course, the main ones are radio and electrical engineering, where tungsten wire goes.
The next one is the manufacture of alloy steels, which are distinguished by their special hardness, elasticity and strength. Added together with chromium to iron, it gives the so-called high-speed steels, which retain their hardness and sharpness even when heated. They are used to make cutters, drills, cutters, as well as other cutting and drilling tools (in general, there is a lot of tungsten in a drilling tool).
Interesting alloys of tungsten with rhenium - high-temperature thermocouples are made from it, operating at temperatures above 2000 ° C, although only in an inert atmosphere.
Well, another interesting application is tungsten welding electrodes for electric welding. Such electrodes are non-consumable and it is necessary to supply another metal wire to the welding site to provide a weld pool. Tungsten electrodes are used in argon-arc welding - for welding non-ferrous metals such as molybdenum, titanium, nickel, as well as high-alloy steels.
As you can see, the production of tungsten is not for ancient times.
And why is there tungsten?
Tungsten can only be obtained with the construction of electrical engineering - with the help of electrical engineering and for electrical engineering.
No electricity - no tungsten, but you don't need it either.