Development of technology for extracting tungsten from stale tailings of the Dzhida VMC Olesya Stanislavovna Artemova. Development of a technology for the extraction of tungsten from the stale tailings of the Dzhida VMC Extraction of tungsten from the tailings of processing plants

25.11.2019

Introduction

1 . Importance of technogenic 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. Study of the material composition and technological properties of stale tailings of the Dzhida VMC

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

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 to work

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 terms of its quality, metal consumption, energy intensity and wear resistance.

more than 12 billion tons of waste, 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.

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, SB. Leonov, L.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 developing 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”.

Objective- scientifically substantiate, develop and test
rational technological methods of enrichment of stale

The following tasks were solved in the work:

Estimate the distribution of tungsten over the entire 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 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;

to 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: 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 are defended main scientific provisions:

The patterns 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 concentration 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. Predictive technological indicators of gravitational enrichment of initial mineral raw materials are determined in different size.

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.

The material composition of mineral raw materials

When examining a secondary tailing dump (emergency dump tailing dump (HAS)) 35 furrow samples were taken from the pits and strippings along the slopes of the dumps; the total length of the furrows is 46 m. The pits and strippings are located in 6 exploration lines, spaced 40-100 m apart from each other; the distance between the pits (cleanings) in the exploration lines is from 30-40 to 100-150 m. All lithological varieties of sands have been tested. The samples were analyzed for the content of W03 and S (II) . In this area, 13 samples were taken from pits 1.0 m deep. The distance between the lines is about 200 m, between the workings - from 40 to 100 m (depending on the distribution of the same type of lithological layer). The results of sample analyzes for the content of WO3 and sulfur are given in Table. 2.1. Table 2.1 - The content of WO3 and sulfide sulfur in private samples of XAS It can be seen that the content of WO3 varies between 0.05-0.09%, with the exception of sample M-16, taken from medium-grained gray sands. In the same sample, high concentrations of S (II) were found - 4.23% and 3.67%. For individual samples (M-8, M-18), a high content of S sulfate was noted (20-30% of the total sulfur content). In the upper part of the emergency tailing dump, 11 samples of various lithological varieties were taken. The content of WO3 and S (II), depending on the origin of the sands, varies in a wide range: from 0.09 to 0.29% and from 0.78 to 5.8%, respectively. Elevated WO3 contents are characteristic of medium-coarse-grained sand varieties. The content of S (VI) is 80 - 82% of the total content of S, but in some samples, mainly with low contents of tungsten trioxide and total sulfur, it decreases to 30%.

The reserves of the deposit can be estimated as resources of category Pj (see Table 2.2). In the upper part of the length of the pit, they vary in a wide range: from 0.7 to 9.0 m, so the average content of controlled components is calculated taking into account the parameters of the pits. In our opinion, based on the above characteristics, taking into account the composition of stale tailings, their safety, conditions of occurrence, contamination with household waste, the content of WO3 in them and the degree of sulfur oxidation, only the upper part of the emergency tailing dump with resources of 1.0 million tons of sands and 1330 tons of WO3 with a WO3 content of 0.126%. Their location in close proximity to the projected processing plant (250-300 m) favors their transportation. The lower part of the emergency tailing dump is to be disposed of as part of the environmental rehabilitation program for the city of Zakamensk.

5 samples were taken on the deposit area. The interval between sampling points is 1000-1250 m. Samples were taken for the entire thickness of the layer, analyzed for the content of WO3, Ptot and S (II) (see Table 2.3). Table 2.3 - The content of WO3 and sulfur in individual ATO samples From the results of the analyzes it can be seen that the content of WO3 is low, varies from 0.04 to 0.10%. The average content of S (II) is 0.12% and is of no practical interest. The work carried out does not allow us to consider the secondary alluvial tailing dump as a potential industrial facility. However, as a source of environmental pollution, these formations are subject to disposal. The main tailing dump (MTF) has been explored along parallel exploration lines oriented along the azimuth of 120 and located 160 - 180 m apart. Exploration lines are oriented across the strike of the dam and the slurry pipeline, through which ore tailings were discharged, deposited subparallel to the dam crest. Thus, the exploration lines were also oriented across the bedding of technogenic deposits. Along the exploration lines, the bulldozer passed trenches to a depth of 3-5 m, from which pits were driven to a depth of 1 to 4 m. The depth of the trenches and pits was limited by the stability of the walls of the workings. The pits in the trenches were driven through 20 - 50 m in the central part of the deposit and after 100 m - on the southeastern flank, on the area of the former settling pond (now dried up), from which water was supplied to the processing plants during the operation of the plant.

The area of the NTO along the distribution border is 1015 thousand m2 (101.5 ha); along the long axis (along the valley of the river Barun-Naryn) it is extended for 1580 m, in the transverse direction (near the dam) its width is 1050 m. Consequently, one pit illuminates an area of 12850 m, which is equivalent to an average network of 130x100 m. all workings); the area of the exploration network averaged 90x100 m2. On the extreme southeastern flank, at the site of a former settling pond in the area of development of fine-grained sediments - silts, 12 pits (15% of the total) were drilled, characterizing an area of about 370 thousand m (37% of the total area of the technogenic deposit); the average network area here was 310x100 m2. In the area of transition from inequigranular sands to silts, composed of silty sands, on an area of about 115 thousand m (11% of the area of the technogenic deposit), 8 pits were passed (10% of the number of workings in the technogenic deposit) and the average area of the exploration network was 145x100 m. of the tested section at the man-caused deposit is 4.3 m, including on uneven-grained sands -5.2 m, silty sands -2.1 m, silts -1.3 m. - 1115 m near the upper part of the dam, up to 1146 - 148 m in the central part and up to 1130-1135 m on the southeastern flank. In total, 60 - 65% of the capacity of the technogenic deposit has been tested. Trenches, pits, clearings and burrows are documented in M 1:50 -1:100 and tested with a furrow with a section of 0.1x0.05 m2 (1999) and 0.05x0.05 m2 (2000). The length of furrow samples was 1 m, weight 10 - 12 kg in 1999. and 4 - 6 kg in 2000. The total length of the tested intervals in the exploration lines was 338 m, in general, taking into account the detailing areas and individual sections outside the network, it was 459 m. The mass of the samples taken was 5 tons.

The samples together with the passport (characteristic of the breed, sample number, production and performer) were packed in polyethylene and then cloth bags and sent to the RAC of the Republic of Buryatia, where they were weighed, dried, analyzed for the content of W03, and S (II) according to the methods of NS AM. The correctness of the analyzes was confirmed by the comparability of the results of ordinary, group (RAC analyses) and technological (TsNIGRI and VIMS analyses) samples. The results of the analysis of individual technological samples taken at the OTO are given in Appendix 1. The main (OTO) and two side tailings (KhAT and ATO) of the Dzhida VMK were statistically compared in terms of WO3 content using Student's t-test (see Appendix 2) . With a confidence probability of 95%, it was established: - no significant statistical difference in the content of WO3 between individual samples of side tailings; - average results of OTO sampling in terms of WO3 content in 1999 and 2000. belong to the same general population. Consequently, the chemical composition of the main tailing dump changes insignificantly over time under the influence of external influences. All stocks of GRT can be processed using a single technology.; - the average results of testing the main and secondary tailings in terms of WO3 content significantly differ from each other. Therefore, the development of a local enrichment technology is required to involve minerals from side tailings.

Technological properties of mineral raw materials

According to the granular composition, the sediments are divided into three types of sediments: inequigranular sands; silty sands (silty); silts. There are gradual transitions between these types of precipitation. More distinct boundaries are observed in the thickness of the section. They are caused by the alternation of sediments of different size composition, different colors (from dark green to light yellow and gray) and different material composition (quartz-feldspar non-metallic part and sulfide with magnetite, hematite, hydroxides of iron and manganese). The entire sequence is layered - from finely to coarsely layered; the latter is more characteristic of coarse-grained deposits or interlayers of essentially sulfide mineralization. Fine-grained (silty, silty fractions, or layers composed of dark-colored - amphibole, hematite, goethite) usually form thin (the first cm - mm) layers. The occurrence of the entire sequence of sediments is subhorizontal with a predominant dip of 1-5 in the northern points. Inequigranular sands are located in the northwestern and central parts of the OTO, which is due to their sedimentation near the source of discharge - the pulp conduit. The width of the strip of uneven-grained sands is 400-500 m, along the strike they occupy the entire width of the valley - 900-1000 m. The color of the sands is gray-yellow, yellow-green. The grain composition is variable - from fine-grained to coarse-grained varieties up to gravelstone lenses with a thickness of 5-20 cm and a length of up to 10-15 m. Silty (silty) sands stand out in the form of a layer 7-10 m thick (horizontal thickness, outcrop 110-120 m ). They lie under uneven-grained sands. In the section, they are a layered stratum of gray, greenish-gray color with alternating fine-grained sands with interlayers of silt. The volume of silts in the section of silty sands increases in the southeast direction, where silts make up the main part of the section.

Silts compose the southeastern part of the OTO and are represented by finer particles of enrichment wastes of dark gray, dark green, bluish-green color with interlayers of grayish-yellow sands. The main feature of their structure is a more homogeneous, more massive texture with less pronounced and less clearly expressed layering. The silts are underlain by silty sands and lie on the base of the bed - alluvial-deluvial deposits. The granulometric characteristics of OTO mineral raw materials with the distribution of gold, tungsten, lead, zinc, copper, fluorite (calcium and fluorine) by size classes are given in Table. 2.8. According to the granulometric analysis, the bulk of the OTO sample material (about 58%) has a particle size 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 less than 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 in the content in size classes from -3 +1 mm to -0.25 + 0.1 mm (0.04-0.05%) 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%. Huebnerite accumulation occurs only in small-sized material, that is, in the -0.1 + 0.044 mm class. Thus, 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%. Differential and integral histograms of the distribution of particles of mineral raw materials OTO by size classes and histograms of the absolute and relative distribution of W by size classes of mineral raw materials OTO are shown in Fig. 2.2. and 2.3. In table. 2.9 shows data on impregnation of hubnerite and scheelite in mineral raw materials OTO of initial size and crushed to - 0.5 mm.

In the class -5 + 3 mm of the original mineral raw material, there are no grains of pobnerite and scheelite, as well as intergrowths. In the -3+1 mm class, the content of free grains of scheelite and hübnerite is quite high (37.2% and 36.1%, respectively). In the -1 + 0.5 mm class, both mineral forms of tungsten are present in almost equal amounts, both in the form of free grains and in the form of intergrowths. In thin classes -0.5 + 0.25, -0.25 + 0.125, -0.125 + 0.063, -0.063 + 0 mm, the content of free grains of scheelite and hübnerite is significantly higher than the content of intergrowths (the content of intergrowths varies from 11.9 to 3, 0%) The size class -1+0.5 mm is boundary and the content of free grains of scheelite and hübnerite and their intergrowths is practically the same in it. Based on the data in Table. 2.9, it can be concluded that it is necessary to classify the deslimed mineral raw materials OTO according to the size of 0.1 mm and separate enrichment of the resulting classes. From a large class, it is necessary to separate free grains into a concentrate, and tailings containing intergrowths must be subjected to regrinding. Crushed and de-sludged tailings should be combined with de-sludged grade -0.1+0.044 of the original mineral raw materials and sent to gravity operation II in order to extract fine grains of scheelite and pobnerite into middlings.

2.3.2 Study of the possibility of radiometric separation of mineral raw materials in the initial size Radiometric separation is a process of large-sized separation of ores according to the content of valuable components, based on the selective effect of various types of radiation on the properties of minerals and chemical elements. More than twenty methods of radiometric enrichment are known; the most promising of them are X-ray radiometric, X-ray luminescent, radio resonance, photometric, autoradiometric and neutron absorption. With the help of radiometric methods, the following technological problems are solved: preliminary enrichment with the removal of waste rock from the ore; selection of technological varieties, varieties with subsequent enrichment according to separate schemes; isolation of products suitable for chemical and metallurgical processing. The assessment of radiometric washability includes two stages: the study of the properties of ores and the experimental determination of the technological parameters of enrichment. At the first stage, the following main properties are studied: the content of valuable and harmful components, particle size distribution, single- and multi-component contrast of the ore. At this stage, the fundamental possibility of using radiometric enrichment is established, the limiting separation indicators are determined (at the stage of contrast study), separation methods and features are selected, their effectiveness is evaluated, theoretical separation indicators are determined, and a schematic diagram of radiometric enrichment is developed, taking into account the specifics of the subsequent processing technology. At the second stage, the modes and practical results of separation are determined, enlarged laboratory tests of the radiometric enrichment scheme are carried out, a rational version of the scheme is selected based on a technical and economic comparison of the combined technology (with radiometric separation at the beginning of the process) with the basic (traditional) technology.

In each case, the mass, size and number of technological samples are set depending on the properties of the ore, the structural features of the deposit and the methods of its exploration. The content of valuable components and the uniformity of their distribution in the ore mass are the determining factors in the use of radiometric enrichment. The choice of the method of radiometric enrichment is influenced by the presence of impurity elements isomorphically associated with useful minerals and in some cases playing the role of indicators, as well as the content of harmful impurities, which can also be used for these purposes.

Optimization of the GR processing scheme

In connection with the involvement in commercial operation of low-grade ores with a tungsten content of 0.3-0.4%, in recent years, multi-stage combined enrichment schemes based on a combination of gravity, flotation, magnetic and electrical separation, chemical finishing of low-grade flotation concentrates, etc. have become widespread. . A special International Congress in 1982 in San Francisco was devoted to the problems of improving the technology of enrichment of low-grade ores. An analysis of the technological schemes of operating enterprises showed that various methods of preliminary concentration have become widespread in ore preparation: photometric sorting, preliminary jigging, enrichment in heavy media, wet and dry magnetic separation. In particular, photometric sorting is effectively used at one of the largest suppliers of tungsten products - at Mount Corbine in Australia, which processes ores with a tungsten content of 0.09% at large Chinese factories - Taishan and Xihuashan.

For preliminary concentration of ore components in heavy media, highly efficient Dinavirpul devices from Sala (Sweden) are used. According to this technology, the material is classified and the +0.5 mm class is enriched in a heavy medium, represented by a mixture of ferrosilicon. Some factories use dry and wet magnetic separation as pre-concentration. So, at the Emerson plant in the USA, wet magnetic separation is used to separate the pyrrhotite and magnetite contained in the ore, and at the Uyudag plant in Turkey, grade - 10 mm is subjected to dry grinding and magnetic separation in separators with low magnetic intensity to separate magnetite, and then enriched in separators with high tension in order to separate the garnet. Further enrichment includes bench concentration, flotation gravity and scheelite flotation. An example of the use of multi-stage combined schemes for the enrichment of poor tungsten ores, which ensure the production of high-quality concentrates, are the technological schemes used at factories in the PRC. So, at the Taishan plant with a capacity of 3000 tons / day for ore, wolframite-scheelite material with a tungsten content of 0.25% is processed. The original ore is subjected to manual and photometric sorting with the removal of 55% of waste rock to the dump. Further enrichment is carried out on jigging machines and concentration tables. The obtained rough gravity concentrates are adjusted by the methods of flotation gravity and flotation. The factories of Xihuashan, which processes ores with a wolframite to scheelite ratio of 10:1, use a similar gravity cycle. The draft gravity concentrate is fed to flotation gravity and flotation, due to which sulphides are removed. Next, wet magnetic separation of the chamber product is carried out in order to isolate wolframite and rare earth minerals. The magnetic fraction is sent to electrostatic separation and then wolframite flotation. The non-magnetic fraction enters the flotation of sulphides, and the flotation tails are subjected to magnetic separation to obtain scheelite and cassiterite-wolframite concentrates. The total content of WO3 is 65% with an extraction of 85%.

There is an increase in the use of the flotation process in combination with the chemical refinement of the resulting poor concentrates. In Canada, at the Mount Pleasant plant for the enrichment of complex tungsten-molybdenum ores, a flotation technology has been adopted, including flotation of sulfides, molybdenite and wolframite. In the main sulfide flotation, copper, molybdenum, lead, and zinc are recovered. The concentrate is cleaned, finely ground, subjected to steaming and conditioning with sodium sulfide. Molybdenum concentrate is cleaned and subjected to acid leaching. Sulfide flotation tailings are treated with sodium fluorosilicone to depress gangue minerals and wolframite is floated with organophosphorus acid, followed by leaching of the resulting wolframite concentrate with sulfuric acid. At the Kantung plant (Canada), the scheelite flotation process is complicated by the presence of talc in the ore, therefore, a primary talc flotation cycle is introduced, then copper minerals and pyrrhotite are flotation. The flotation tailings are subjected to gravity enrichment to obtain two tungsten concentrates. Gravity tailings are sent to the scheelite flotation cycle, and the resulting flotation concentrate is treated with hydrochloric acid. At the Ikssheberg plant (Sweden), the replacement of the gravity-flotation scheme with a purely flotation one made it possible to obtain a scheelite concentrate with a content of 68-70% WO3 with a recovery of 90% (according to the gravity-flotation scheme, the recovery was 50%) . Recently, much attention has been paid to improving the technology of extracting tungsten minerals from sludge in two main areas: gravitational sludge enrichment in modern multi-deck concentrators (similar to tin-containing sludge enrichment) with subsequent refinement of the concentrate by flotation and enrichment in wet magnetic separators with a high magnetic field strength (for wolframite slimes).

An example of the use of combined technology are factories in China. The technology includes slime thickening to 25-30% solids, sulphide flotation, tailings enrichment in centrifugal separators. The crude concentrate obtained (WO3 content 24.3% with a recovery of 55.8%) is fed to wolframite flotation using organophosphorus acid as a collector. The flotation concentrate containing 45% WO3 is subjected to wet magnetic separation to obtain wolframite and tin concentrates. According to this technology, a wolframite concentrate with a content of 61.3% WO3 is obtained from sludge with a content of 0.3-0.4% WO3 with a recovery of 61.6%. Thus, technological schemes for the enrichment of tungsten ores are aimed at increasing the complexity of the use of raw materials and separating all associated valuable components into independent types of products. So, at the factory Kuda (Japan), when enriching complex ores, 6 marketable products are obtained. In order to determine the possibility of additional extraction of useful components from stale tailings in the mid-90s. in TsNIGRI, a technological sample with a tungsten trioxide content of 0.1% was studied. It has been established that the main valuable component in the tailings is tungsten. The content of non-ferrous metals is quite low: copper 0.01-0.03; lead - 0.09-0.2; zinc -0.06-0.15%, gold and silver were not found in the sample. The conducted studies have shown that for the successful extraction of tungsten trioxide, significant costs will be required for regrinding tailings, and at this stage, their involvement in processing is not promising.

The technological scheme of mineral processing, which includes two or more devices, embodies all the characteristic features of a complex object, and the optimization of the technological scheme can, apparently, be the main task of system analysis. In solving this problem, almost all the previously considered modeling and optimization methods can be used. However, the structure of concentrator circuits is so complex that additional optimization techniques need to be considered. Indeed, for a circuit consisting of at least 10-12 devices, it is difficult to implement a conventional factorial experiment or to carry out multiple nonlinear statistical processing. Currently, several ways to optimize circuits are outlined, an evolutionary way of summarizing the accumulated experience and taking a step in the successful direction of changing the circuit.

Semi-industrial testing of the developed technological scheme for the enrichment of general relativity and industrial plant

The tests were carried out in October-November 2003. During the tests, 15 tons of initial mineral raw materials were processed in 24 hours. The results of testing the developed technological scheme are shown in fig. 3.4 and 3.5 and in table. 3.6. It can be seen that the yield of the conditioned concentrate is 0.14%, the content is 62.7% with the extraction of WO3 49.875%. The results of spectral analysis of a representative sample of the obtained concentrate, are given in table. 3.7, confirm that the W-concentrate of the III magnetic separation is conditioned and corresponds to the grade KVG (T) of GOST 213-73 "Technical requirements (composition,%) for tungsten concentrates obtained from tungsten-containing ores". Therefore, the developed technological scheme for the extraction of W from the stale tailings of the Dzhida VMK ore beneficiation can be recommended for industrial use and the stale tailings are transferred into additional industrial mineral raw materials of the Dzhida VMK.

For the industrial processing of stale tailings according to the developed technology at Q = 400 t/h, a list of equipment has been developed, which is given in class -0.1 mm must be carried out on a KNELSON centrifugal separator with periodic discharge of the concentrate. Thus, it has been established that the most effective way to extract WO3 from RTO with a particle size of -3 + 0.5 mm is screw separation; from size classes -0.5 + 0.1 and -0.1 + 0 mm and crushed to -0.1 mm tailings of primary enrichment - centrifugal separation. The essential features of the technology for processing stale tailings of the Dzhida VMK are as follows: 1. A narrow classification of the feed sent for primary enrichment and refinement is necessary; 2. An individual approach is required when choosing the method of primary enrichment of classes of various sizes; 3. Obtaining tailings is possible with the primary enrichment of the finest feed (-0.1 + 0.02 mm); 4. Use of hydrocyclone operations to combine dehydration and sizing operations. The drain contains particles with a particle size of -0.02 mm; 5. Compact arrangement of equipment. 6. Profitability of the technological scheme (APPENDIX 4), the final product is a conditioned concentrate that meets the requirements of GOST 213-73.

Kiselev, Mikhail Yurievich

Magnetic methods are widely used in the enrichment of ores of ferrous, non-ferrous and rare metals and in other areas of industry, including food. They are used for beneficiation of iron, manganese, copper-nickel tungsten ores, as well as for finishing concentrates of rare metal ores, regeneration of ferromagnetic weighting agents in separation plants in heavy suspensions, for removing iron impurities from quartz sands, pyrite from coal, etc.

All minerals are different in specific magnetic susceptibility, and for the extraction of weakly magnetic minerals, fields with high magnetic characteristics are required in the working zone of the separator.

In ores of rare metals, in particular tungsten and niobium and tantalum, the main minerals in the form of wolframite and columbite-tantalite have magnetic properties and it is possible to use high-gradient magnetic separation with extraction of ore minerals into the magnetic fraction.

In the laboratory of magnetic enrichment methods NPO ERGA, tests were carried out on tungsten and niobium-tantalum ore of the Spoykoininsky and Orlovsky deposits. For dry magnetic separation, a roller separator SMVI manufactured by NPO ERGA was used.

The separation of tungsten and niobium-tantalum ore was carried out according to scheme No. 1. The results are presented in the table.

Based on the results of the work, the following conclusions can be drawn:

The content of useful components in the separation tails is: WO3 according to the first separation scheme - 0.031±0.011%, according to the second - 0.048±0.013%; Ta 2 O 5 and Nb 2 O 5 -0.005±0.003%. This suggests that the induction in the working zone of the separator is sufficient to extract weakly magnetic minerals into the magnetic fraction, and the magnetic separator of the SMVI type is suitable for obtaining tailings.

Tests of the SMVI magnetic separator were also carried out on baddeleyite ore in order to extract weakly magnetic iron minerals (hematite) into tailings and purify zirconium concentrate.

The separation resulted in a reduction in the iron content in the non-magnetic product from 5.39% to 0.63% with a recovery of 93%. The content of zirconium in the concentrate increased by 12%.

The separator operation scheme is shown in Fig. one

The use of the SMVI magnetic separator has found wide application in the enrichment of various ores. SMVI can serve both as the main enrichment equipment and as a refinement of concentrates. This is confirmed by successful semi-industrial tests of this equipment.

Tungsten minerals, ores and concentrates

Tungsten is a rare element, its average content in the earth's crust is Yu-4% (by mass). About 15 minerals of tungsten are known, however, only minerals of the wolframite group and scheelite are of practical importance.

Wolframite (Fe, Mn)WO4 is an isomorphic mixture (solid solution) of iron and manganese tungstates. If there is more than 80% iron tungstate in the mineral, the mineral is called ferberite, in the case of the predominance of manganese tungstate (more than 80%) - hübnerite. Mixtures lying in composition between these limits are called wolframites. Minerals of the wolframite group are colored black or brown and have a high density (7D-7.9 g/cm3) and a hardness of 5-5.5 on the mineralogical scale. The mineral contains 76.3-76.8% W03. Wolframite is weakly magnetic.

Scheelite CaWOA is calcium tungstate. The color of the mineral is white, gray, yellow, brown. Density 5.9-6.1 g/cm3, hardness according to the mineralogical scale 4.5-5. Scheelite often contains an isomorphic admixture of powellite, CaMo04. When irradiated with ultraviolet rays, scheelite fluoresces blue - blue light. At a molybdenum content of more than 1%, fluorescence becomes yellow. Scheelite is non-magnetic.

Tungsten ores are usually poor in tungsten. The minimum content of W03 in ores, at which their exploitation is profitable, is currently 0.14-0.15% for large and 0.4-0.5% for small deposits.

Together with tungsten minerals, molybdenite, cassiterite, pyrite, arsenopyrite, chalcopyrite, tantalite or columbite, etc. are found in ores.

According to the mineralogical composition, two types of deposits are distinguished - wolframite and scheelite, and according to the shape of ore formations - vein and contact types.

In vein deposits, tungsten minerals mostly occur in quartz veins of small thickness (0.3-1 m). The contact type of deposits is associated with zones of contact between granite rocks and limestones. They are characterized by deposits of scheelite-bearing skarn (skarns are silicified limestones). The skarn-type ores include the Tyrny-Auzskoye deposit, the largest in the USSR, in the North Caucasus. During the weathering of vein deposits, wolframite and scheelite accumulate, forming placers. In the latter, wolframite is often combined with cassiterite.

Tungsten ores are enriched to obtain standard concentrates containing 55-65% W03. A high degree of enrichment of wolframite ores is achieved using various methods: gravity, flotation, magnetic and electrostatic separation.

When enriching scheelite ores, gravity-flotation or purely flotation schemes are used.

The extraction of tungsten into conditioned concentrates during the enrichment of tungsten ores ranges from 65-70% to 85-90%.

When enriching complex or difficult-to-enrich ores, it is sometimes economically advantageous to remove intermediate products with a content of 10-20% W03 from the enrichment cycle for chemical (hydrometallurgical) processing, as a result of which "artificial scheelite" or technical tungsten trioxide is obtained. Such combined schemes provide a high extraction of tungsten from ores.

The state standard (GOST 213-73) provides for the content of W03 in tungsten concentrates of the 1st grade not less than 65%, the 2nd grade - not less than 60%. They limit the content of impurities P, S, As, Sn, Cu, Pb, Sb, Bi in the range from hundredths of a percent to 1.0%, depending on the grade and purpose of the concentrate.

As of 1981, the explored reserves of tungsten are estimated at 2903 thousand tons, of which 1360 thousand tons are in the PRC. The USSR, Canada, Australia, the USA, South and North Korea, Bolivia, Brazil, and Portugal have significant reserves. Production of tungsten concentrates in capitalist and developing countries in the period 1971 - 1985 fluctuated within 20 - 25 thousand tons (in terms of metal content).

Methods for processing tungsten concentrates

The main product of the direct processing of tungsten concentrates (in addition to ferrotungsten, smelted for the needs of ferrous metallurgy) is tungsten trioxide. It serves as the starting material for tungsten and tungsten carbide, the main constituent of hard alloys.

Production schemes for the processing of tungsten concentrates are divided into two groups depending on the accepted method of decomposition:

Tungsten concentrates are sintered with soda or treated with aqueous soda solutions in autoclaves. Tungsten concentrates are sometimes decomposed with aqueous solutions of sodium hydroxide.

Concentrates are decomposed by acids.

In cases where alkaline reagents are used for decomposition, solutions of sodium tungstate are obtained, from which, after purification from impurities, end products are produced - ammonium paratungstate (PVA) or tungstic acid. 24

When the concentrate is decomposed by acids, precipitation of technical tungstic acid is obtained, which is purified from impurities in subsequent operations.

Decomposition of tungsten concentrates. alkaline reagents Sintering with Na2C03

Sintering wolframite with Na2C03. The interaction of wolframite with soda in the presence of oxygen proceeds actively at 800-900 C and is described by the following reactions: 2FeW04 + 2Na2C03 + l/202 = 2Na2W04 + Fe203 + 2C02; (l) 3MnW04 + 3Na2C03 + l/202 = 3Na2W04 + Mn304 + 3C02. (2)

These reactions proceed with a large loss of Gibbs energy and are practically irreversible. With the ratio in wolframite FeO:MnO = i:i AG ° 1001C = -260 kJ / mol. With an excess of Na2C03 in the charge of 10-15% in excess of the stoichiometric amount, complete decomposition of the concentrate is achieved. To accelerate the oxidation of iron and manganese, sometimes 1-4% nitrate is added to the charge.

Sintering wolframite with Na2C03 at domestic enterprises is carried out in tubular rotary kilns lined with fireclay bricks. In order to avoid the melting of the charge and the formation of deposits (growths) in the zones of the furnace with a lower temperature, tailings from the leaching of cakes (containing iron and manganese oxides) are added to the charge, reducing the content of W03 in it to 20-22%.

The furnace, 20 m long and with an outer diameter of 2.2 m, at a rotation speed of 0.4 rpm and an inclination of 3, has a capacity of 25 t/day in terms of charge.

The components of the charge (crushed concentrate, Na2C03, saltpeter) are fed from the hoppers to the screw mixer using automatic scales. The mixture enters the furnace hopper, from which it is fed into the furnace. After exiting the kiln, the sinter pieces pass through the crushing rolls and the wet grinding mill, from which the pulp is sent to the upper polisher (Fig. 1).

Scheelite sintering with Na2C03. At temperatures of 800-900 C, the interaction of scheelite with Na2C03 can proceed according to two reactions:

CaW04 + Na2CQ3 Na2W04 + CaCO3; (1.3)

CaW04 + Na2C03 *=*■ Na2W04 + CaO + C02. (1.4)

Both reactions proceed with a relatively small change in the Gibbs energy.

Reaction (1.4) proceeds to an appreciable extent above 850 C, when decomposition of CaCO3 is observed. The presence of calcium oxide in the sinter leads, when the sinter is leached with water, to the formation of poorly soluble calcium tungstate, which reduces the extraction of tungsten into solution:

Na2W04 + Ca(OH)2 = CaW04 + 2NaOH. (1.5)

With a large excess of Na2CO3 in the charge, this reaction is largely suppressed by the interaction of Na2CO4 with Ca(OH)2 to form CaCO3.

To reduce the consumption of Na2C03 and prevent the formation of free calcium oxide, quartz sand is added to the mixture to bind calcium oxide into insoluble silicates:

2CaW04 + 2Na2C03 + Si02 = 2Na2W04 + Ca2Si04 + 2C02;(l.6) AG°100IC = -106.5 kJ.

Nevertheless, in this case, too, to ensure a high degree of tungsten recovery into the solution, a significant excess of Na2CO3 (50–100% of the stoichiometric amount) must be introduced into the charge.

The sintering of the scheelite concentrate charge with Na2C03 and quartz sand is carried out in drum furnaces, as described above for wolframite at 850–900°C. To prevent melting, leaching dumps (containing mainly calcium silicate) are added to the charge at the rate of reducing the content of W03 to 20-22%.

Leaching of soda specks. When cakes are leached with water, sodium tungstate and soluble salts of impurities (Na2Si03, Na2HP04, Na2HAs04, Na2Mo04, Na2S04), as well as an excess of Na2C03, pass into the solution. Leaching is carried out at 80-90 ° C in steel reactors with mechanical agitation, operating in hierio-

Concentrates with soda:

Elevator feeding the concentrate to the mill; 2 - ball mill operating in a closed cycle with an air separator; 3 - auger; 4 - air separator; 5 - bag filter; 6 - automatic weight dispensers; 7 - conveying auger; 8 - screw mixer; 9 - charge hopper; 10 - feeder;

Drum oven; 12 - roll crusher; 13 - rod mill-leacher; 14 - reactor with stirrer

Wild mode, or continuous drum rotary lixiviators. The latter are filled with crushing rods for crushing pieces of cake.

The extraction of tungsten from the sinter into the solution is 98-99%. Strong solutions contain 150-200 g/l W03.

Autoclave o-c One method of decomposition of tungsten concentrates

The autoclave-soda method was proposed and developed in the USSR1 in relation to the processing of scheelite concentrates and middlings. Currently, the method is used in a number of domestic factories and in foreign countries.

The decomposition of scheelite with Na2C03 solutions is based on the exchange reaction

CaW04CrB)+Na2C03(pacTB)^Na2W04(pacTB)+CaC03(TB). (1.7)

At 200-225 °C and the corresponding excess of Na2C03, depending on the composition of the concentrate, decomposition proceeds with sufficient speed and completeness. The concentration equilibrium constants of reaction (1.7) are small, increase with temperature, and depend on the soda equivalent (i.e., the number of moles of Na2C03 per 1 mole of CaW04).

With a soda equivalent of 1 and 2 at 225 C, the equilibrium constant (Kc = C / C cq) is 1.56 and

0.99 respectively. From this it follows that at 225 C the minimum required soda equivalent is 2 (i.e., the excess of Na2C03 is 100%). The actual excess of Na2C03 is higher, since the rate of the process slows down as equilibrium is approached. For scheelite concentrates with a content of 45-55% W03 at 225 C, a soda equivalent of 2.6-3 is required. For middlings containing 15-20% W03, 4-4.5 moles of Na2C03 per 1 mole of CaW04 are required.

CaCO3 films formed on scheelite particles are porous and up to a thickness of 0.1–0.13 mm their influence on the rate of scheelite decomposition by Na2CO3 solutions was not found. With intensive stirring, the rate of the process is determined by the rate of the chemical stage, which is confirmed by the high value of the apparent activation energy E = 75+84 kJ/mol. However, in case of insufficient stirring speed (which

Occurs in horizontal rotating autoclaves), an intermediate regime is realized: the rate of the process is determined both by the rate of supply of the reagent to the surface and the rate of chemical interaction.

0.2 0.3 0, it 0.5 0.5 0.7 0.8

As can be seen from Fig. 2, the specific reaction rate decreases approximately in inverse proportion to the increase in the ratio of molar concentrations of Na2W04:Na2C03 in solution. This is

Ryas. Fig. 2. Dependence of the specific rate of decomposition of scheelite by a soda solution in an autoclave j on the molar ratio of Na2W04/Na2C03 concentrations in the solution at

Causes the need for a significant excess of Na2C03 against the minimum required, determined by the value of the equilibrium constant. To reduce the consumption of Na2C03, a two-stage countercurrent leaching is carried out. In this case, the tailings after the first leaching, in which there is little tungsten (15-20% of the original), are treated with a fresh solution containing a large excess of Na2C03. The resulting solution, which is circulating, enters the first stage of leaching.

Decomposition with Na2C03 solutions in autoclaves is also used for wolframite concentrates, however, the reaction in this case is more complicated, since it is accompanied by hydrolytic decomposition of iron carbonate (manganese carbonate is only partially hydrolyzed). The decomposition of wolframite at 200-225 °C can be represented by the following reactions:

MnW04(TB)+Na2C03(paCT)^MiiC03(TB)+Na2W04(paCTB); (1.8)

FeW04(TB)+NaC03(pacT)*=iFeC03(TB)+Na2W04(paCTB); (1.9)

FeC03 + HjO^FeO + H2CO3; (1.10)

Na2C03 + H2C03 = 2NaHC03. (l. ll)

The resulting iron oxide FeO at 200-225 ° C undergoes a transformation according to the reaction:

3FeO + H20 = Fe304 + H2.

The formation of sodium bicarbonate leads to a decrease in the concentration of Na2CO3 in the solution and requires a large excess of the reagent.

To achieve satisfactory decomposition of wolframite concentrates, it is necessary to grind them finely and increase the consumption of Na2C03 to 3.5-4.5 g-eq, depending on the composition of the concentrate. High-manganese wolframites are more difficult to decompose.

The addition of NaOH or CaO to the autoclaved slurry (which leads to causticization of Na2C03) improves the degree of decomposition.

The decomposition rate of wolframite can be increased by introducing oxygen (air) into the autoclave pulp, which oxidizes Fe (II) and Mil (II), which leads to the destruction of the crystal lattice of the mineral on the reacting surface.

secondary steam

Ryas. 3. Autoclave unit with a horizontally rotating autoclave: 1 - autoclave; 2 - loading pipe for the pulp (steam is introduced through it); 3 - pulp pump; 4 - pressure gauge; 5 - pulp reactor-heater; 6 - self-evaporator; 7 - drop separator; 8 - pulp input into the self-evaporator; 9 - chipper made of armored steel; 10 - pipe for pulp removal; 11 - pulp collector

Leaching is carried out in steel horizontal rotating autoclaves heated with live steam (Fig. 3) and vertical continuous autoclaves with stirring of the pulp with bubbling steam. Approximate process mode: temperature 225 pressure in the autoclave ~2.5 MPa, ratio T:W=1:(3.5*4), duration at each stage 2-4 hours.

Figure 4 shows a diagram of an autoclave battery. The initial autoclave pulp, heated by steam to 80-100 °C, is pumped into autoclaves, where it is heated to

secondary steam

Ditch. Fig. 4. Scheme of a continuous autoclave plant: 1 - reactor for heating the initial pulp; 2 - piston pump; 3 - autoclave; 4 - throttle; 5 - self-evaporator; 6 - pulp collector

200-225 °C live steam. In continuous operation, the pressure in the autoclave is maintained by discharging the slurry through a throttle (calibrated carbide washer). The pulp enters the self-evaporator - a vessel under pressure of 0.15-0.2 MPa, where the pulp is rapidly cooled due to intensive evaporation. The advantages of autoclave-soda decomposition of scheelite concentrates before sintering are the exclusion of the furnace process and a somewhat lower content of impurities in tungsten solutions (especially phosphorus and arsenic).

The disadvantages of the method include a large consumption of Na2C03. A high concentration of excess Na2C03 (80-120 g/l) entails an increased consumption of acids for the neutralization of solutions and, accordingly, high costs for the disposal of waste solutions.

Decomposition of tungstate conc.

Sodium hydroxide solutions decompose wolframite according to the exchange reaction:

Me WC>4 + 2Na0Hi=tNa2W04 + Me(0 H)2, (1.13)

Where Me is iron, manganese.

The value of the concentration constant of this reaction Kc = 2 at temperatures of 90, 120 and 150 °C is equal to 0.68, respectively; 2.23 and 2.27.

Complete decomposition (98-99%) is achieved by treating the finely divided concentrate with 25-40% sodium hydroxide solution at 110-120°C. The required excess of alkali is 50% or more. The decomposition is carried out in steel sealed reactors equipped with stirrers. The passage of air into the solution accelerates the process due to the oxidation of iron (II) hydroxide Fe (OH) 2 into hydrated iron (III) oxide Fe203-«H20 and manganese (II) hydroxide Mn (OH) 2 into hydrated manganese (IV) oxide Mn02-lH20 .

The use of decomposition with alkali solutions is advisable only for high-grade wolframite concentrates (65-70% W02) with a small amount of silica and silicate impurities. When processing low-grade concentrates, highly contaminated solutions and hard-to-filter precipitates are obtained.

Processing of sodium tungstate solutions

Solutions of sodium tungstate containing 80-150 g/l W03, in order to obtain tungsten trioxide of the required purity, have so far been mainly processed according to the traditional scheme, which includes: purification from compounds of impurity elements (Si, P, As, F, Mo); precipitation

Calcium tungsten mag (artificial scheelite) with its subsequent decomposition with acids and obtaining technical tungstic acid; dissolution of tungstic acid in ammonia water, followed by evaporation of the solution and crystallization of ammonium paratungstate (PVA); calcination of PVA to obtain pure tungsten trioxide.

The main drawback of the scheme is its multi-stage nature, carrying out most of the operations in a periodic mode, and the duration of a number of redistributions. An extraction and ion-exchange technology for converting Na2W04 solutions into (NH4)2W04 solutions has been developed and is already being used at some enterprises. The main redistributions of the traditional scheme and new extraction and ion-exchange variants of the technology are briefly considered below.

Purification of impurities

Silicon cleaning. When the content of Si02 in solutions exceeds 0.1% of the content of W03, preliminary purification from silicon is necessary. Purification is based on the hydrolytic decomposition of Na2Si03 by boiling a solution neutralized to pH=8*9 with the release of silicic acid.

The solutions are neutralized with hydrochloric acid, added in a thin stream with stirring (to avoid local peroxidation) to a heated solution of sodium tungstate.

Purification of phosphorus and arsenic. To remove phosphate and arsenate ions, the method of precipitation of ammonium-magnesium salts Mg (NH4) P04 6H20 and Mg (NH4) AsC) 4 6H20 is used. The solubility of these salts in water at 20 C is 0.058 and 0.038%, respectively. In the presence of an excess of Mg2+ and NH4 ions, the solubility is lower.

The precipitation of phosphorus and arsenic impurities is carried out in the cold:

Na2HP04 + MgCl2 + NH4OH = Mg(NH4)P04 + 2NaCl +

Na2HAsQ4 + MgCl2 + NH4OH = Mg(NH4)AsQ4 + 2NaCl +

After a long standing (48 hours), crystalline precipitates of ammonium-magnesium salts precipitate from the solution.

Purification from fluoride ions. With a high content of fluorite in the original concentrate, the content of fluoride ions reaches 5 g/L. Solutions are purified from fluoride - ions by precipitation with magnesium fluoride from a neutralized solution, to which MgCl2 is added. Purification of fluorine can be combined with hydrolytic isolation of silicic acid.

Molybdenum cleaning. Solutions of sodium tungstate" must be purified from molybdenum if its content exceeds 0.1% of the W03 content (i.e. 0.1-0.2 t / l). At a molybdenum concentration of 5-10 g / l ( for example, in the processing of scheelite-powellite Tyrny-Auzsky concentrates), the isolation of molybdenum is of particular importance, since it is aimed at obtaining a molybdenum chemical concentrate.

A common method is to precipitate the sparingly soluble molybdenum trisulfide MoS3 from a solution.

It is known that when sodium sulfide is added to solutions of tungstate or sodium molybdate, sulfosalts Na23S4 or oxosulfosalts Na23Sx04_x (where E is Mo or W) are formed:

Na2304 + 4NaHS = Na23S4 + 4NaOH. (1.16)

The equilibrium constant of this reaction for Na2Mo04 is much larger than for Na2W04(^^0 » Kzr). Therefore, if an amount of Na2S is added to the solution, sufficient only for interaction with Na2Mo04 (with a slight excess), then molybdenum sulfosalt is predominantly formed. With the subsequent acidification of the solution to pH = 2.5 * 3.0, the sulfosalt is destroyed with the release of molybdenum trisulfide:

Na2MoS4 + 2HC1 = MoS3 j + 2NaCl + H2S. (1.17)

Oxosulfosalts decompose with the release of oxosulfides (for example, MoSjO, etc.). Together with molybdenum trisulfide, a certain amount of tungsten trisulfide co-precipitates. By dissolving the sulfide precipitate in a soda solution and re-precipitating molybdenum trisulfide, a molybdenum concentrate is obtained with a W03 content of not more than 2% with a loss of tungsten 0.3-0.5% of the initial amount.

After partial oxidative roasting of the precipitate of molybdenum trisulfide (at 450-500 ° C), a molybdenum chemical concentrate is obtained with a content of 50-52% molybdenum.

The disadvantage of the method of precipitation of molybdenum in the composition of trisulfide is the release of hydrogen sulfide according to reaction (1.17), which requires expenses for the neutralization of gases (they use the absorption of H2S in a scrubber irrigated with a sodium hydroxide solution). The selection of molybdenum trisulfide is carried out from a solution heated to 75-80 C. The operation is carried out in sealed steel reactors, gummed or coated with acid-resistant enamel. The trisulfide precipitates are separated from the solution by filtration on a filter press.

Obtaining tungstic acid from solutions of sodium tungstate

Tungstic acid can be directly isolated from a solution of sodium tungstate with hydrochloric or nitric acid. However, this method is rarely used due to the difficulty of washing precipitates from sodium ions, the content of which in tungsten trioxide is limited.

For the most part, calcium tungstate is initially precipitated from the solution, which is then decomposed with acids. Calcium tungstate is precipitated by adding a CaCl2 solution heated to 80-90 C to a sodium tungstate solution with a residual alkalinity of the solution of 0.3-0.7%. In this case, a white finely crystalline, easily settled precipitate falls out, sodium ions remain in the mother liquor, which ensures their low content in tungstic acid. 99-99.5% W precipitates from the solution, mother solutions contain 0.05-0.07 g/l W03. The CaW04 precipitate washed with water in the form of a paste or pulp enters for decomposition with hydrochloric acid when heated to 90 °:

CaW04 + 2HC1 = H2W04i + CaCl2. (1.18)

During decomposition, a high final acidity of the pulp is maintained (90–100 g/l HCI), which ensures the separation of tungstic acid from impurities of phosphorus, arsenic, and partly molybdenum compounds (molybdic acid dissolves in hydrochloric acid). Precipitates of tungstic acid require thorough washing from impurities (especially from calcium salts

and sodium). In recent years, continuous washing of tungstic acid in pulsating columns has been mastered, which greatly simplified the operation.

At one of the enterprises in the USSR, when processing sodium tungstate solutions, instead of hydrochloric acid, nitric acid is used to neutralize the solutions and decompose CaW04 precipitates, and the precipitation of the latter is carried out by introducing Ca(N03)2 into the solutions. In this case, the nitric acid mother liquors are disposed of, obtaining nitrate salts used as fertilizer.

Purification of technical tungstic acid and obtaining W03

Technical tungstic acid, obtained by the method described above, contains 0.2-0.3% impurities. As a result of acid calcination at 500-600 C, tungsten trioxide is obtained, suitable for the production of hard alloys based on tungsten carbide. However, the production of tungsten requires trioxide of a higher purity with a total impurity content of no more than 0.05%.

The ammonia method for purifying tungstic acid is generally accepted. It is easily soluble in ammonia water, while most of the impurities remain in the sediment: silica, iron and manganese hydroxides, and calcium (in the form of CaW04). However, ammonia solutions may contain an admixture of molybdenum, alkali metal salts.

From the ammonia solution, as a result of evaporation and subsequent cooling, a crystalline precipitate of PVA is isolated:

Evaporation

12(NH4)2W04 * (NH4)10H2W12O42 4Н20 + 14NH3 +

In industrial practice, the composition of PVA is often written in the oxide form: 5(NH4)20-12W03-5H20, which does not reflect its chemical nature as an isopoly acid salt.

Evaporation is carried out in batch or continuous devices made of stainless steel. Usually 75-80% of tungsten is isolated into crystals. Deeper crystallization is undesirable in order to avoid contamination of the crystals with impurities. It is significant that most of the molybdenum impurity (70-80%) remains in the mother liquor. From the mother liquor enriched with impurities, tungsten is precipitated in the form of CaW04 or H2W04, which is returned to the appropriate stages of the production scheme.

PVA crystals are squeezed out on a filter, then in a centrifuge, washed with cold water and dried.

Tungsten trioxide is obtained by thermal decomposition of tungstic acid or PVA:

H2W04 \u003d "W03 + H20;

(NH4) 10H2W12O42 4H20 = 12W03 + 10NH3 + 10H20. (1.20)

Calcination is carried out in rotary electric furnaces with a pipe made of heat-resistant steel 20X23H18. The calcination mode depends on the purpose of tungsten trioxide, the required size of its particles. So, to obtain tungsten wire grade VA (see below), PVA is calcined at 500-550 ° C, wire grades VCh and VT (tungsten without additives) - at 800-850 ° C.

Tungstic acid is calcined at 750-850 °C. Tungsten trioxide derived from PVA has larger particles than trioxide derived from tungstic acid. In tungsten trioxide, intended for the production of tungsten, the content of W03 must be at least 99.95% for the production of hard alloys - at least 99.9%.

Extraction and ion-exchange methods for processing solutions of sodium tungstate

The processing of sodium tungstate solutions is greatly simplified when tungsten is extracted from solutions by extraction with an organic extractant, followed by re-extraction from the organic phase with an ammonia solution with separation of PVA from an ammonia solution.

Since in a wide range of pH=7.5+2.0 tungsten is found in solutions in the form of polymeric anions, anion-exchange extractants are used for extraction: salts of amines or quaternary ammonium bases. In particular, the sulfate salt of trioctylamine (i?3NH)HS04 (where R is С8Н17) is used in industrial practice. The highest rates of tungsten extraction are observed at pH=2*4.

Extraction is described by the equation:

4 (i? 3NH) HS04 (opr) + H2 \ U120 * "(aq) + 2H + (aq) ї \u003d ї

Ї \u003d ї (D3GSh) 4H4 \ U12O40 (org) + 4H80; (aq.). (l.2l)

The amine is dissolved in kerosene, to which a technical mixture of polyhydric alcohols (C7 - C9) is added to prevent the precipitation of a solid phase (due to the low solubility of amine salts in kerosene). The approximate composition of the organic phase: amines 10%, alcohols 15%, kerosene - the rest.

Solutions purified from mrlibden, as well as impurities of phosphorus, arsenic, silicon and fluorine, are sent for extraction.

Tungsten is re-extracted from the organic phase with ammonia water (3-4% NH3), obtaining solutions of ammonium tungstate, from which PVA is isolated by evaporation and crystallization. The extraction is carried out in mixer-settler type apparatuses or in pulsating columns with packing.

The advantages of extraction processing of sodium tungstate solutions are obvious: the number of operations of the technological scheme is reduced, it is possible to carry out a continuous process for obtaining ammonium tungstate solutions from sodium tungstate solutions, and production areas are reduced.

Wastewater from the extraction process may contain an admixture of 80-100 mg/l of amines, as well as impurities of higher alcohols and kerosene. To remove these environmentally harmful impurities, froth flotation and adsorption on activated carbon are used.

Extraction technology is used at foreign enterprises and is also implemented at domestic plants.

The use of ion-exchange resins is a direction of the scheme for processing sodium tungstate solutions that competes with extraction. For this purpose, low-basic anion exchangers containing amine groups (often tertiary amines) or amphoteric resins (ampholytes) containing carboxyl and amine groups are used. At pH=2.5+3.5, tungsten polyanions are sorbed on resins, and for some resins the total capacity is 1700-1900 mg W03 per 1 g of resin. In the case of resin in the 8C>5~ form, sorption and elution are described by the equations, respectively:

2tf2S04 + H4W12044; 5^"4H4W12O40 + 2SOf; (1.22)

I?4H4WI2O40 + 24NH4OH = 12(NH4)2W04 + 4DON + 12H20. (l.23)

The ion-exchange method was developed and applied at one of the enterprises of the USSR. The required contact time of the resin with the solution is 8-12 hours. The process is carried out in a cascade of ion-exchange columns with a suspended resin bed in a continuous mode. A complicating circumstance is the partial separation of PVA crystals at the stage of elution, which requires their separation from the resin particles. As a result of elution, solutions containing 150–170 g/l of W03 are obtained, which are fed to the evaporation and crystallization of PVA.

The disadvantage of ion-exchange technology compared to extraction is the unfavorable kinetics (contact time 8-12 hours versus 5-10 minutes for extraction). At the same time, the advantages of ion exchangers include the absence of waste solutions containing organic impurities, as well as the fire safety and non-toxicity of resins.

Decomposition of scheelite concentrates with acids

In industrial practice, mainly in the processing of high-grade scheelite concentrates (70-75% W03), direct decomposition of scheelite with hydrochloric acid is used.

Decomposition reaction:

CaW04 + 2HC1 = W03H20 + CoCl2 (1.24)

Almost irreversible. However, the acid consumption is much higher than the stoichiometrically required one (250–300%) due to the inhibition of the process by tungstic acid films on scheelite particles.

The decomposition is carried out in sealed reactors with stirrers, lined with acid-resistant enamel and heated through a steam jacket. The process is carried out at 100-110 C. The duration of decomposition varies from 4-6 to 12 hours, which depends on the degree of grinding, as well as the origin of the concentrate (scheelites of various deposits differ in reactivity).

A single treatment does not always lead to a complete opening. In this case, after dissolving tungstic acid in ammonia water, the residue is re-treated with hydrochloric acid.

During the decomposition of scheelite-powellite concentrates with a content of 4-5% molybdenum, most of the molybdenum passes into the hydrochloric acid solution, which is explained by the high solubility of molybdic acid in hydrochloric acid. So, at 20 C in 270 g/l HC1, the solubilities of H2Mo04 and H2WO4 are 182 and 0.03 g/l, respectively. Despite this, complete separation of molybdenum is not achieved. Precipitates of tungstic acid contain 0.2-0.3% molybdenum, which cannot be extracted by re-treatment with hydrochloric acid.

The acid method differs from the alkaline methods of scheelite decomposition by a smaller number of operations of the technological scheme. However, when processing concentrates with a relatively low content of W03 (50-55%) with a significant content of impurities, in order to obtain conditioned ammonium paratungstate, two or three ammonia purifications of tungstic acid have to be carried out, which is uneconomical. Therefore, decomposition with hydrochloric acid is mostly used in the processing of rich and pure scheelite concentrates.

The disadvantages of the method of decomposition with hydrochloric acid are the high consumption of acid, the large volume of waste solutions of calcium chloride and the complexity of their disposal.

In the light of the tasks of creating waste-free technologies, the nitric acid method of decomposition of scheelite concentrates is of interest. In this case, the mother solutions are easy to dispose of, obtaining nitrate salts.

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.

Ore beneficiation waste storage sites 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 the 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 secondary 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 a 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 tests 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 in order to extract 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 "Plaksin 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"

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.

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 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.

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 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 patterns of gravitational concentration 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.

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.

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 stale tailings of the Dzhida VMK ore enrichment made it possible to obtain a conditioned W-concentrate, solve the problem of depletion of 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 in order to extract tungsten was 0.55 years.

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The invention relates to a method for the complex processing of tailings for the enrichment of tungsten-containing ores. The method includes their classification into fine and coarse fractions, screw separation of the fine fraction to obtain a tungsten product and its repurification. At the same time, recleaning is carried out on a screw separator to obtain a crude tungsten concentrate, which is subjected to finishing on concentration tables to obtain a gravitational tungsten concentrate, which is subjected to flotation to obtain a high-grade conditioned tungsten concentrate and a sulfide-containing product. The tails of the screw separator and the concentration table are combined and subjected to thickening. At the same time, the drain obtained after thickening is fed to the classification of tailings for the enrichment of tungsten-containing ores, and the thickened product is subjected to enrichment on a screw separator to obtain secondary tailings and a tungsten product, which is sent for cleaning. The technical result is to increase the depth of processing of tailings for the enrichment of tungsten-containing ores. 1 z.p. f-ly, 1 tab., 1 ill.

The invention relates to the enrichment of minerals and can be used in the processing of tailings enrichment of tungsten-containing ores.

When processing tungsten-containing ores, as well as tailings for their enrichment, gravity, flotation, magnetic, as well as electrostatic, hydrometallurgical and other methods are used (see, for example, Burt P.O., with the participation of K. Mills. Gravitational enrichment technology. Translated from English. - M.: Nedra, 1990). So, for the preliminary concentration of useful components (mineral raw materials), photometric and lumometric sorting are used (for example, the Mount Carbine and King Island processing plants), enrichment in heavy media (for example, the Portuguese Panasquera factory and the English Hemerdan factory). ), jigging (especially poor raw materials), magnetic separation in a weak magnetic field (for example, to isolate pyrite, pyrrhotite) or high-intensity magnetic separation (to separate wolframite and cassiterite).

For the processing of tungsten-containing sludge, it is known to use flotation, in particular, wolframite in the PRC and at the Canadian Mount Plisad factory, and in some factories flotation has completely replaced gravity enrichment (for example, the Jokberg factories, Sweden and Mittersil, Austria).

It is also known to use screw separators and screw locks for the enrichment of tungsten-containing ores, old dumps, stale tailings, and sludge.

So, for example, when processing old dumps of tungsten ore at the Cherdoyak factory (Kazakhstan), the initial dump material after crushing and grinding to a fineness of 3 mm was enriched in jigging machines, the undersize product of which was then cleaned on a concentration table. The technological scheme also included enrichment on screw separators, on which 75-77% WO 3 was extracted with an output of enrichment products of 25-30%. Screw separation made it possible to increase the extraction of WO 3 by 3-4% (see, for example, Anikin M.F., Ivanov V.D., Pevzner M.L. "Screw separators for ore dressing", Moscow, publishing house "Nedra ", 1970, 132 p.).

The disadvantages of the technological scheme for processing old dumps are the high load at the head of the process for the jigging operation, the insufficiently high extraction of WO 3 and the significant yield of enrichment products.

A known method of associated production of tungsten concentrate by processing molybdenite flotation tailings (factory "Climax molybdenum", Canada). Tailings containing tungsten are separated by means of a screw separation into tungsten tailings (light fraction), primary wolframite - cassiterite concentrate. The latter is subjected to hydrocyclone and the sludge discharge is sent to tailings, and the sand fraction is sent to the flotation separation of pyrite concentrate containing 50% S (sulfides) and its output to tailings. The chamber product of sulfide flotation is cleaned using a screw separation and/or cones to obtain waste pyrite-containing tailings and a wolframite-cassiterite concentrate, which is processed on concentration tables. At the same time, wolframite-cassiterite concentrate and tailings are obtained. The crude concentrate after dehydration is re-cleaned sequentially by cleaning it from iron using magnetic separation, flotation removal of monazite from it (phosphate flotation) and then dehydrated, dried, classified and separated using staged magnetic separation into a concentrate with a content of 65% WO 3 after stage I and 68% WO 3 after stage II. Also get a non-magnetic product - tin (cassiterite) concentrate containing ~35% tin.

This method of processing is characterized by disadvantages - complexity and multi-stage, as well as high energy intensity.

There is a known method for additional extraction of tungsten from the tailings of gravity enrichment (factory "Boulder", USA). The tailings of gravity enrichment are crushed, deslimed in a classifier, the sands of which are separated on hydraulic classifiers. The resulting classes are enriched separately on concentration tables. Coarse-grained tailings are returned to the grinding cycle, and fine tailings are thickened and re-enriched on slurry tables to obtain a finished concentrate, middling product for regrinding, and tailings sent for flotation. The rougher flotation concentrate is subjected to one cleaning. The original ore contains 0.3-0.5% WO 3 ; the extraction of tungsten reaches 97%, with about 70% of the tungsten being recovered by flotation. However, the content of tungsten in the flotation concentrate is low (about 10% WO 3) (see, Polkin S.I., Adamov E.V. Enrichment of non-ferrous metal ores. Textbook for universities. M., Nedra, 1983, 213 pp.)

The disadvantages of the technological scheme for the processing of tailings of gravity enrichment are the high load at the head of the process on the enrichment operation on concentration tables, multi-operation, low quality of the resulting concentrate.

A known method of processing scheelite-containing tailings in order to remove hazardous materials from them and process non-hazardous and ore minerals using an improved separation process (separation) (KR 20030089109, SNAE et al., 21.11.2003). The method includes the stages of homogenizing mixing of scheelite-containing tailings, introduction of the pulp into the reactor, “filtration” of the pulp with a screen to remove various foreign materials, subsequent separation of the pulp by screw separation, thickening and dehydration of non-metallic minerals to obtain a cake, drying the cake in a rotary dryer, crushing dry cake using a hammer mill operating in a closed cycle with a screen, separation of crushed minerals using a “micron” separator into fractions of small and coarse grains (granules), as well as magnetic separation of a coarse-grained fraction to obtain magnetic minerals and a non-magnetic fraction containing scheelite. The disadvantage of this method is multi-operation, the use of energy-intensive drying of wet cake.

There is a known method of additional extraction of tungsten from the tailings of the processing plant of the Ingichka mine (see A.B. Ezhkov, Kh.T. v.1, MISiS, M., 2001). The method includes preparation of the pulp and its desliming in a hydrocyclone (class removal - 0.05 mm), subsequent separation of the deslimed pulp in a cone separator, two-stage recleaning of the cone separator concentrate on concentration tables to obtain a concentrate containing 20.6% WO 3 , with an average recovery 29.06%. The disadvantages of this method are the low quality of the resulting concentrate and insufficiently high extraction of WO 3 .

The results of studies on the gravitational enrichment of the tailings of the Ingichkinskaya enrichment plant are described (see S.V. » // Mining Bulletin of Uzbekistan, 2008, No. 3).

The closest to the patented technical solution is a method for extracting tungsten from stale tailings of enrichment of tungsten-containing ores (Artemova O.S. Development of a technology for extracting tungsten from stale tailings of the Dzhida VMK. Abstract of the thesis of a candidate of technical sciences, Irkutsk State Technical University, Irkutsk, 2004 - prototype).

The technology for extracting tungsten from stale tailings according to this method includes the operations of obtaining a rough tungsten-containing concentrate and middling product, a gold-bearing product and secondary tailings using gravitational methods of wet enrichment - screw and centrifugal separation - and subsequent finishing of the obtained rough concentrate and middling product using gravity (centrifugal) enrichment and magnetic separation to obtain a standard tungsten concentrate containing 62.7% WO 3 with the extraction of 49.9% WO 3 .

According to this method, stale tails are subjected to primary classification with the release of 44.5% of the mass. into secondary tailings in the form of a fraction of +3 mm. The -3 mm tailings fraction is divided into -0.5 and +0.5 mm classes, and from the latter, a coarse concentrate and tails are obtained using screw separation. The fraction -0.5 mm is divided into classes -0.1 and +0.1 mm. From the +0.1 mm class, a coarse concentrate is isolated by centrifugal separation, which, like the coarse screw separation concentrate, is subjected to centrifugal separation to obtain a crude tungsten concentrate and a gold-bearing product. The tailings of the screw and centrifugal separation are crushed to -0.1 mm in a closed cycle with classification and then divided into classes -0.1 + 0.02 and -0.02 mm. The -0.02 mm class is removed from the process as secondary waste tailings. Class -0.1+0.02 mm is enriched by centrifugal separation to obtain secondary waste tailings and tungsten middlings, sent for refining by magnetic separation together with centrifugal separation concentrate, finely ground to -0.1 mm. In this case, a tungsten concentrate (magnetic fraction) and middlings (non-magnetic fraction) are obtained. The latter is subjected to magnetic separation II with the release of a non-magnetic fraction into secondary tailings and a tungsten concentrate (magnetic fraction), which is enriched sequentially by centrifugal, magnetic and again centrifugal separation to obtain a conditioned tungsten concentrate with a content of 62.7% WO 3 at an output of 0.14 % and recovery of 49.9%. At the same time, the tailings of centrifugal separations and the non-magnetic fraction are sent to the secondary waste tailings, the total output of which at the stage of finishing the crude tungsten concentrate is 3.28% with a content of 2.1% WO 3 in them.

The disadvantages of this method are the multi-operation process, which includes 6 classification operations, 2 regrinding operations, as well as 5 centrifugal operations and 3 magnetic separation operations using relatively expensive apparatus. At the same time, the refinement of the crude tungsten concentrate to the standard is associated with the production of secondary tailings with a relatively high content of tungsten (2.1% WO 3).

The objective of the present invention is to improve the method of processing tailings, including stale dump tailings for enrichment of tungsten-containing ores, to obtain a high-grade tungsten concentrate and a sulfide-containing product along with a decrease in the content of tungsten in secondary tailings.

The patented method for the complex processing of tailings for the enrichment of tungsten-containing ores includes the classification of tailings into fine and coarse fractions, screw separation of the fine fraction to obtain a tungsten product, repurification of the tungsten product, and finishing to obtain a high-grade tungsten concentrate, a sulfide-containing product and secondary waste tailings.

The method differs in that the resulting tungsten product is subjected to recleaning on a screw separator to obtain a rough concentrate and tailings, a rough concentrate is subjected to finishing on concentration tables to obtain a gravitational tungsten concentrate and tailings. The tailings of the concentration table and the cleaning screw separator are combined and subjected to thickening, then the thickening discharge is fed to the classification stage at the head of the technological scheme, and the thickened product is enriched on a screw separator to obtain secondary waste tailings and a tungsten product, which is sent for cleaning. Gravity tungsten concentrate is subjected to flotation to obtain a high-grade standard tungsten concentrate (62% WO 3) and a sulfide-containing product, which is processed by known methods.

The method can be characterized by the fact that the tailings are classified into fractions, mainly +8 mm and -8 mm.

The technical result of the patented method is to increase the depth of processing while reducing the number of technological operations and the load on them due to the separation in the head of the process of the bulk of the initial tailings (more than 90%) into secondary tailings, using a simpler design and operation of energy-saving screw separation technology. This dramatically reduces the load on subsequent enrichment operations, as well as capital and operating costs, which ensures the optimization of the enrichment process.

The effectiveness of the patented method is shown on the example of complex processing of tailings of the Ingichkinskaya enrichment plant (see drawing).

Processing begins with the classification of tailings into small and large fractions with the separation of secondary tailings in the form of a large fraction. The fine fraction of the tailings is subjected to screw separation with the separation in the head of the technological process into the secondary tailings of the bulk of the original tailings (more than 90%). This makes it possible to drastically reduce the load on subsequent operations, capital costs and operating costs accordingly.

The resulting tungsten product is subjected to recleaning on a screw separator to obtain a crude concentrate and tailings. The crude concentrate is subjected to refinement on concentration tables to obtain gravity tungsten concentrate and tailings.

The tailings of the concentration table and the cleaning screw separator are combined and subjected to thickening, for example, in a thickener, mechanical classifier, hydrocyclone and other apparatuses. The thickening drain is fed to the classification stage at the head of the technological scheme, and the thickened product is enriched on a screw separator to obtain secondary tailings and a tungsten product, which is sent for cleaning.

Gravity tungsten concentrate is brought by flotation to high-grade conditional tungsten concentrate (62% WO 3 ) to obtain a sulfide-containing product.

Thus, high-grade (62% WO 3 ) conditioned tungsten concentrate is isolated from tungsten-containing tailings upon reaching a relatively high WO 3 recovery of ~49% and a relatively low tungsten content (0.04% WO 3 ) in secondary waste tailings.

The resulting sulfide-containing product is processed in a known manner, for example, it is used to produce sulfuric acid and sulfur, and is also used as a corrective additive in the production of cements.

High-grade conditioned tungsten concentrate is a highly liquid marketable product.

As follows from the results of the implementation of the patented method on the example of stale tailings for the enrichment of tungsten-containing ores of the Ingichkinskaya concentrator, its effectiveness is shown in comparison with the prototype method (see table). EFFECT: additional obtaining of a sulfide-containing product, reduction of the volume of fresh water consumed due to the creation of water circulation is provided. It creates the possibility of processing significantly poorer tailings (0.09% WO 3), a significant reduction in the content of tungsten in the secondary tailings (up to 0.04% WO 3). In addition, the number of technological operations has been reduced and the load on most of them has been reduced due to the separation of the bulk of the initial tailings (more than 90%) in the head of the technological process into secondary tailings, using a simpler and less energy-intensive screw separation technology, which reduces capital costs for the purchase of equipment and operating costs.

1. A method for the complex processing of tailings for the enrichment of tungsten-containing ores, including their classification into fine and coarse fractions, screw separation of the fine fraction to obtain a tungsten product, its cleaning and finishing to obtain a high-grade tungsten concentrate, a sulfide-containing product and secondary tailings, characterized in that the obtained after screw separation, the tungsten product is subjected to recleaning on a screw separator to obtain a crude tungsten concentrate, the resulting crude tungsten concentrate is subjected to finishing on concentration tables to obtain a gravity tungsten concentrate, which is subjected to flotation to obtain a high-grade conditioned tungsten concentrate and a sulfide-containing product, tails of a screw separator and a concentration table combined and subjected to thickening, the drain obtained after thickening is fed to the classification of tailings for the enrichment of tungsten-containing ores, and the subjected to enrichment on a screw separator to obtain secondary tailings and a tungsten product, which is sent for cleaning.