RU2100095C1 - Method of bulk flotation of sulfides containing noble metals from complex-ore iron-containing materials - Google Patents

Abstract

FIELD: mineral dressing. SUBSTANCE: flotation concentration of iron materials containing complex-ore sulfides and noble metal minerals can be used in combined processes of concentration for recovering heavy, nonferrous, and noble metals from low-grade iron sulfide-containing metallurgical products into bulk sulfide concentrate. Method includes preliminarily preparing material for flotation, adding to slurry petrochemical oil-soluble sulfur-containing reagent and sulfhydryl collector, and isolation of useful metals into foam product - bulk sulfide concentrate. As above- mentioned reagent, sulfonic acids and alkali-earth metal sulfonates are used, their weight ratio to sulfhydryl collector being (0.005- 0.10):1. Above-mentioned sulfonates can be used in the form of detergent-dispersing additives for basic lube oils or as components of commercial petroleum products, as well as components of exhausted motor oils. EFFECT: enhanced efficiency of process. 3 cl, 1 tbl

Description

 The invention relates to flotation concentration of ferrous materials containing polymetallic sulfides and noble metal minerals, and can be used in combined enrichment processes to extract heavy non-ferrous and noble metals from poor ferrous sulfide-containing metallurgical products into a collective sulfide concentrate.

где R и R_i углеводородные радикалы, M K⁺ или Na⁺ (Шубов Л. Я. Иванков С. И. Щеглова Н. К. Флотационные реагенты в процессах обогащения минерального сырья. Справочник в 2 кн./Под ред. Л. В. Кондратьевой. М. Недра, 1990, кн. 1, с. 84);
формальдегид-сульфоксилат натрия (там же, с. 99);
тритиокарбонаты, водорастворимые производные ксантогеновых кислот, водорастворимые производные тио- и дитиокарбаминовых кислот, производные тиофосфатных кислот (там же, с. 99 109);
водорастворимые соединения со смешанными функциональными группами, например тиоамиды (там же, с. 117 137);
водорастворимые гетероциклы и их производные (там же, с. 137 145);
лаурилпиридинийсульфат (там же, с. 39).Achieving high performance in the field of mineral processing is largely dependent on the improvement of reagent flotation regimes. The decisive role in increasing the efficiency of reagent modes belongs to reagent-gatherers [1]
For flotation of complex materials containing polymetallic sulfides and inclusion of noble metals, the most effective combination is a sulfhydryl collector with an organic sulfur-containing reagent that enhances the collector's flotation activity [2]
Known methods for flotation concentration of ferrous ores and products of their processing containing polymetallic sulfides and noble metals associated with sulfides, including preliminary preparation of the starting material for flotation, conditioning pulp with a sulfhydryl collector and a sulfur-containing organic water-soluble reagent, and subsequent flotation separation of valuable metals into a collective sulfide concentrate in which as a sulfur-containing organic reagent, providing increased completeness of target recovery of nonferrous and noble metals, are used
dialkyldithiocarbamates (alkaline salts of dithiocarbamic acid) of the formula

where R and R _{i are} hydrocarbon radicals, MK ⁺ or Na ⁺ (Shubov L. Ya. Ivankov S.I. Shcheglova N.K. Flotation reagents in the processes of mineral processing. Handbook in 2 books / Ed. by L.V. Kondratieva, M. Nedra, 1990, book 1, p. 84);
sodium formaldehyde sulfoxylate (ibid., p. 99);
tritiocarbonates, water-soluble derivatives of xanthogen acids, water-soluble derivatives of thio- and dithiocarbamic acids, derivatives of thiophosphate acids (ibid., p. 99 109);
water-soluble compounds with mixed functional groups, for example thioamides (ibid., p. 117 137);
water-soluble heterocycles and their derivatives (ibid., p. 137 145);
lauryl pyridinium sulfate (ibid., p. 39).

 The above analogues have one drawback: all of them are relatively ineffective in the flotation of aggregates, which limits the possibility of their use in the collective flotation cycle. The use of known methods in the processes of enrichment of coarsely ground mineral raw materials or in the presence of coarse dispersed polymineral formations of secondary origin in the flotation feed (for example, sulfur sulfide aggregates in pulps of autoclave - chemical enrichment of ferronickel pyrrhotite concentrates) causes increased losses of valuable metals with dump tailings. The need for deeper grinding of the initial ore significantly increases energy costs during its pulp preparation and increases dust removal in the cycle of subsequent pyrometallurgical processing of the obtained concentrates.

 Another significant disadvantage of the known methods is their lack of complexity and lack of universality in relation to the flotation of minerals of precious metals. As a rule, their effect is quite selective and strongly depends on the characteristics of the raw material being enriched and the specific conditions for its enrichment. In particular, the use of well-known methods in the enrichment technology for products of processing sulfide copper - nickel ores (slag of autogenous processes, pyrrhotite concentrates) containing the entire spectrum of platinum group metals gold and silver is economically unjustified due to the loss of platinum satellite metals with dump iron products.

 In addition, high enrichment of mineral raw materials in the known methods are achieved by expensive methods: increasing the consumption of sulfhydryl collector and the transition to the use of xanthates with a longer hydrocarbon radical (amyl, hexyl). This significantly increases the cost of the enrichment cycle and limits the possibility of increasing the production efficiency of heavy non-ferrous and precious metals.

или углеводородный радикал, замещенный одним или более галоидным простым эфиром или углеводородным тиоэфирным фрагментами; R₂- алифатическая, ароматическая группа или их сочетание (авт. св. N 1582978, кл. B 03 D 1/02, 1990, Б И. N 28);
нефтяные сульфиды алкилтиоцикланы и тиоалканы с небольшим количеством арилсульфатов и гомологов тиофена (Шубов Л. Я. и др. Флотационные реагенты. с. 90);
соединения типа диалкилполисульфидов формулы R₁-S-R₂, где R₁ метил, этил, эпокси, такой замещенный одним или более галоидным простым эфиром или углеводородным тиоэфирным фрагментами; R₂ - алифатическая, циклоалифатическая, ароматическая группа или их сочетание (авт. св. N 1582978, кл. B 03 D 1/02, 1990, Б И. N 28);
соединения типа диалкилполисульфидов формулы R₁-S_x-R₂, где x 2 8 (Шубов Л. Я. и др. Флотационные реагенты. с. 90 91);
продукт обработки нефтяного сульфоксида сернистым газом (там же, с. 92);
ксантогенформиаты маслообразные эфиры ксантогеновых кислот, диксантогенид, минереки и др. (там же, с. 100 103).Known methods for flotation of polymetallic sulfides from complex ferrous materials containing heavy non-ferrous and noble metals, in which flotation uses a combination of a sulfohydryl collector with a water-soluble sulfur-containing organic reagent that enhances the collector's flotation activity. As an additional sulfur-containing reagent used
an organic sulfide of the formula R _i —SR ₂ where R _{1 is} methyl, ethyl, epoxy, such as a group

or a hydrocarbon radical substituted with one or more halide ethers or hydrocarbon thioether moieties; R ₂ is an aliphatic, aromatic group or a combination thereof (ed. St. N 1582978, class B 03 D 1/02, 1990, B I. N 28);
petroleum sulfides alkylthiocyclanes and thioalkanes with a small amount of aryl sulfates and thiophene homologs (Shubov L. Ya. et al. Flotation reagents. p. 90);
compounds of the type of dialkyl polysulfides of the formula R ₁ -SR ₂ where R _{1 is} methyl, ethyl, epoxy, such substituted with one or more halide ethers or hydrocarbon thioether moieties; R ₂ is an aliphatic, cycloaliphatic, aromatic group or a combination thereof (ed. St. N 1582978, class B 03 D 1/02, 1990, B I. N 28);
compounds of the type of dialkyl polysulfides of the formula R ₁ -S _x -R ₂ where x 2 8 (Shubov L. Ya. et al. Flotation reagents. p. 90 91);
a product of the processing of petroleum sulfoxide with sulfur dioxide (ibid., p. 92);
xanthogenformates, oily xanthogenic acid esters, dixanthogenide, minarek, etc. (ibid., p. 100 103).

 A common disadvantage of this group of known methods is the insufficiently high extraction of non-ferrous and noble metals, especially during flotation of sludge ores, finely ground materials and highly dispersed sulfide neoplasms. This is due to the fact that the considered combinations of reagents do not provide active flotation of thin sludge (less than 20 microns). This factor is of particular importance in the flotation of metallurgical products obtained in combined processes. So, for example, in the technology of chemical enrichment of nickel-pyrrhotite concentrates (according to the autoclave oxidative leaching scheme deposition of flotation), newly formed sulfides subjected to flotation obtained using a polysulfide-thiosulfate precipitator have a fineness in the range from 5 to 20 μm. This also caused a low recovery of noble metals represented in the sludge by isomorphic impurities and having ultra-thin inclusions of intrinsic minerals in the source material (for example, inclusions of the platinum and palladium minerals in pyrrhotite ores).

 An important disadvantage of the known methods based on the use of organic sulfides, polysulfides and sulfoxides is the presence of strong foaming properties of these compounds. The combination of strongly expressed collecting and foaming properties in one reagent significantly complicates the control of the flotation process and excludes the possibility of implementing an optimally balanced reagent mode.

 In addition, the disadvantages of the known methods include the increased consumption of sulfhydryl collector, especially when flotating such refractory iron oxide objects as finely ground slags of smelting metallurgical units and acidic pulps of chemical enrichment of ferronickel pyrrhotite concentrates.

 The closest to the proposed method for the totality of the characteristics and the achieved result is a flotation enrichment method for pyrrhotite products containing heavy non-ferrous and platinum metals, including preliminary preparation of the material for flotation, conditioning pulp with a sulfhydryl collector, an additional oil-organic oil-soluble reagent containing natural organosulfur compounds, and isolation precious metals and sulfur in the foam product collective concentrate, and iron in the iron guide atnye tails. In the known method as an additional oil-organic oil-soluble reagent containing organosulfur compounds, oil adsorption resins are used. To increase the efficiency of the collecting action of adsorption resins, they are introduced into the process in diluents or as part of a commercial fuel oil of motor fuel [3]. The preliminary preparation of the pyrrhotite product for flotation involves autoclaved hydrochemical oxidation of ferrosulfides, in which heavy non-ferrous metals partially pass into solution, and sulfide sulfur into elemental form, and subsequent precipitation of non-ferrous metals from solution in the form of secondary polymetallic sulfides (Goryachkin V.I. Nelen I.M. neerson J. M. et al. hydrometallurgical processing of copper-nickel based concentrates autoclave oxidative leaching // Hydrometallurgy, pressure leaching, sorption, extraction / ed. BN Laskorin M. Science, 1976, pp. 48 59).

 Oil adsorption resins are an extract of natural organosulfur compounds. The presence in the resins of sulfur and other heteroatomic compounds determines their high polarity and surface activity, far exceeding the polarity and activity of hydrocarbons (Chertkov Ya. B. Non-hydrocarbon compounds in petroleum products. M. Chemistry, 1964). The industrial use of petroleum adsorption resins in combination with butyl xanthate in the combined technology of autoclave-flotation concentration of pyrrhotite concentrates emitted in the processing cycle of continuous sulfide ores allowed to increase the completeness of extraction into collective sulfide concentrate, 0.5 nickel; platinum 5; palladium 5; rhodium 8.5; gold 6.7; silver 8.9. Moreover, ≈ 20% rel. consumption of butyl xanthate decreased (Improving the technical level and production efficiency of processing pyrrhotite concentrates during the development of the second stage of GMP NM3 // Research Report of Gintsvetmet Institute / t. 2. Isolation of sulfonated product. GRT N 01870059719, topic N 2-87-010 , p. IV. M. November 1988, p. 80 82).

A significant disadvantage of the prototype is its lack of complexity in relation to platinum group metals, especially satellite metals (rhodium, ruthenium, iridium and osmium). So, for example, the average total loss of precious metals with oval tails of the enrichment technology of pyrrhotite products in the known method is 30 35% with a loss level of rare platinum metals of 50 70%
Another important disadvantage of this method is the failure of the collecting action of oil adsorption resins due to the heterogeneity of their composition. Resins of various oils vary significantly in average molecular weight (from 450 to 1500 cu), heteroatomic organosulfur content and class ratios of sulfur compounds contained in resins (Aksanova E.I. Magaril R.Z. Petroleum Chemistry. Tyumen. TSU 1981, p. 91). In addition, the oils of various fields vary greatly in the content of adsorption resins, which is 5 to 10 wt. however, there are highly resinous oils with a content of up to 20 30 wt. (Sablina Z. A. Composition and chemical stability of motor fuels. M. Chemistry, 1972, p. 22 47). It follows that when using adsorption resins in the composition of marketable petroleum products (for example, motor fuel), the flotation activity of the collective action of the latter will vary greatly depending on the characteristics of the source oil field, despite the close similarity of all chemotological and other characteristics regulated by GOST.

 In addition, the disadvantage of this method is the relatively high consumption of adsorption resins having a high molecular weight (up to 1100 cu) hydrocarbon "skeleton". This, on the one hand, complicates the possibility of implementing a closed technological water circulation, since during the long-term operation of this method there is a risk of accumulation of heavy organics in the reverse water, on the other hand, an increased consumption of adsorption resins reduces the performance of subsequent selective flotation (for example, when copper-molybdenum is separated, lead-zinc and other collective concentrates), leads to an overuse of modifier reagents and impairs the quality of the target products. The implementation of the methods at moderate consumption of adsorption resins significantly reduces its effectiveness, especially in the flotation of materials characterized by the presence of particles of extreme sizes of flotation size (thin sludge and coarse aggregates). At the same time, the consumption of sulfohydryl collector increases and the loss of mineral forms of precious metals increases due to their increasing adsorption by gangue minerals and ferrous deposits.

 The objective of the invention is to increase the extraction of valuable metals in a collective sulfide concentrate and at the same time reduce the consumption of sulfhydryl collector by increasing the flotation activity of the collector.

 The problem is solved in that in the method of collective flotation of sulfides containing noble metals from polymetallic iron-containing materials, including preliminary preparation of the material for flotation, introducing an oil-soluble oil-soluble sulfur-containing reagent and sulfhydryl collector into the pulp and recovering valuable metals into the collective sulfide concentrate foam product, according to sulphonic acid is used as an oil-soluble, sulfur-containing reagent alkaline earth metal sulfonates and / or their salts in a mass ratio with a sulfhydryl collector (0.005 - 0.10): 1, respectively.

 Another difference is that inorganic oil-soluble alkaline earth metal sulfonates are used in the form of detergent-dispersant additives to base lubricating oils or as part of marketable petroleum products containing them.

 Another difference of the method is that the oil-organic soluble alkaline earth metal sulfonates are used in the composition of used automobile oils.

 Sulfonic acids are sulfonation products of alkyl aromatic hydrocarbons of petroleum or synthetic origin. In industrial conditions, oleum, concentrated sulfuric anhydride (gaseous or liquid) and air-gas mixtures containing 7 to 8 vol.% Are used as a sulfonating agent. sulfuric anhydride (Kuliev A.M. Chemistry and technology of additives to oils and fuels. L. Chemistry, 1985, p. 66 71).

 The main method for producing sulfonates is the neutralization (saponification) of sulfonic acids with oxides or hydroxides of alkali and alkaline earth metals. Depending on the nature of the feedstock, sulfonates, like sulfonic acids, are divided into petroleum and synthetic.

The solubility of sulfonic acids and sulfonates in solvents of different polarity depends on the molecular weight of the feedstock. In this regard, they are divided into 3 groups:
water soluble ("green") soluble in water and insoluble in petroleum oil;
oil-soluble ("red") soluble in oil and insoluble in water;
water-soluble, intermediate between “green” and “red” and soluble in both polar and hydrocarbon solvents (Sadykhov K.I. Agaev A. N. Sulfonate additives to lubricating oils. Baku. Elm, 1982, p. 6 7; Halperin A.E. Production of additives to motor and transmission oils. M. Chemistry, 1974, p. 86 87).

 Of the three groups of sulfo compounds mentioned in the flotation enrichment of minerals, it is known to use only water- and water-oil-soluble sulfonic acids and their alkali metal salts.

 The use of water- and water-oil-soluble sulfo compounds as collector reagents for flotation of sulfide materials is ineffective (L. Shubov and other Flotation reagents. Reference: 1990, p. 17). In addition, some representatives of the group of "green" sulfonates exhibit strong depressing properties in relation to the flotation of sulfides of heavy non-ferrous metals. So, for example, sulfonates, which form the basis of chromium azo dyes, are used in the processing of copper-zinc ores (ed. St. N 1058137, class B 03 D 1/02, with priority from 01/13/82, and lignosulfonates obtained as a by-product cellulose production, are a potent non-selective depressant of sulfides of copper, nickel and cobalt (Mantsevich M.I. Malinsky R.A. Shcherbakov V.A. et al. // Non-ferrous metals, N 1, 1983, p. 77 - 79).

 Oil-soluble sulfonic acids in their properties differ significantly from water- and water-oil-soluble analogues. They are obtained only from heavy petroleum distillates having a molecular weight of at least 400 cu Commodity sulfonic compounds of this group are obtained on the basis of oily distillates which have undergone selective purification and dewaxing, i.e. from AS-6, DS-8 oils, as well as from residual selective purified MS-20 oil, its fractions or a mixture of distillate oils with MS-20 (Schekhter Yu. N. Krein S. E. Surfactants from petroleum feedstocks. M. Chemistry, 1971, p. 13).

Of the various groups of aromatic hydrocarbons (light, medium, and heavy), light hydrocarbons with mono- and bicyclic alkyl aromatic hydrocarbons with long paraffinic or naphthenic chains (C ₁₆ and higher) with a high viscosity index are most suitable for producing oil-soluble sulfonic acids and their salts. Multicore (polycyclic) aromatic hydrocarbons with short side chains produce green (oil-insoluble) sulfonic acids upon sulfidation (A. Halperin. Production of additives. 1974, p. 87; Kuliev A. M. Chemistry and technology of additives. 1985, p. 69 )

 Oil-soluble sulfonates are obtained by neutralizing “red” sulfonic acids with hydroxides of alkaline earth metals: calcium, magnesium, barium and strontium. Sulfonates of this group are widely used as detergents, detergents and dispersants for motor oils, designed to reduce the formation of carbon deposits on parts of internal combustion engines (Sadikhov K.I. et al. Sulfonate additives. 1982, p. 7).

 In the process of creating the invention, it was found that, in contrast to water- and water-soluble sulfonic compounds, oil-soluble sulfonic acids and red alkaline earth metal sulfonates have the ability to form hydrophobic films on the surface of polymetallic sulfides and their own noble metal minerals, contributing to an increase in their flotation activity.

 An analysis of the scientific, technical and patent literature shows that the technological properties of sulfonic acids and their sulfosalts are determined not so much by the nature of the functional group, by the nature of the feedstock, but by the structure and molecular weight of the hydrocarbon radical * the spatial orientation of the sulfo group in the molecule of these compounds and the valence state of the metal attached to functional group. A clear illustration of this fact is a comparison of the properties of the water-soluble salt of lignosulfonic acids and the oil-soluble salt of petroleum sulfonic acids: the first sharply inhibits the flotation of sulfides, the second acts in the exact opposite.

 The studies revealed a correlation between the effectiveness of the collective action of oil-soluble sulfo compounds and their molecular weight. With an increase in the molecular weight of sulfonic acids and sulfonates (i.e., with an increase in the number of carbon atoms in the alkyl chain), along with an increase in their solubility in petroleum oils and an improvement in detergent-dispersant properties (K. Sadykov and other Sulfonate additives. 1982, p. 6) the collective flotation activity of “red” sulfo compounds is also noticeably enhanced.

 It was experimentally established that the use of oil-soluble sulfonic acids and alkaline earth metal sulfonates in combination with sulfohydryl collectors is accompanied by a synergistic effect, which manifests itself in the fact that the collective effect of this combination of reagents turns out to be greater than could be expected from their additive effect. Studies of flotation of a wide range of polymetallic materials, carried out at various ratios of oil-soluble sulfo compounds and sulfhydryl collectors, have shown that the independent use of red sulfonic acids and sulfonates is significantly inferior to the prototype in terms of basic technological parameters. According to experimental data, the optimal ratio for flotation is the mass ratio of the costs of the oil-soluble sulfo compound and sulfohydryl collector from 0.005: 1 to 0.10: 1, regardless of the nature and chemical-mineralogical composition of the enriched mineral raw materials. Outside this range, the results of using the method are sharply reduced: when the reagent ratio is less than 0.005: 1 (oil-soluble sulfonic compounds less than 0.005 parts), the extraction of non-ferrous and noble metals in the collective sulfide concentrate is lower than in the prototype, and the consumption of sulfhydryl collector rises to the level characteristic of the regime its self use. With a reagent ratio of more than 0.10: 1, the recovery of valuable metals and the consumption of sulfhydryl collector improve slightly, while the quality of the concentrate decreases sharply due to the transition to the foam product of gangue components and iron compounds. In addition, with an increased consumption of oil-soluble sulfo compounds, difficulties arise in the separation of minerals in the cycle of subsequent selective flotation and the problem of closed technological water circulation is aggravated.

In the proposed method, oil-soluble sulfonic acids can be used independently in the form of a refined concentrate or as part of a sulfonated oil product with an initial molecular weight of at least 400 units Heavy distillate oils, motor fuels for low-speed diesels (according to GOST 1667-68 of the DT and DM grades), fuel oils diluted with fuel distillates, etc. can serve as raw materials for the production of “red” sulfonic acids. In the conditions of metallurgical production, it is rational for sulfonation of hydrocarbon products use the contact gases of plants to produce sulfuric acid (5 7 vol. SO ₃ or “strong” process gases of melting units (for example, gases from the Vanyukov furnace) after the catalytic oxidation of sulfur dioxide to SO ₃ .

 Oil-soluble sulfonates of alkaline earth metals are preferably used in the form of industrially produced detergent-dispersant additives for motor oils, for example SB-3 (GOST 101534 -78), PMSya (calcium GOST 12418-66), PMSya (barium, TU 38101574-75), SK- 3 (TU 38101111-71), S-300 (TU 38101444-74), DP-4 (TU 0257-003-13230476-94), etc. The table shows the flotation results using 2 additional organic sulfur-containing reagents samples of sulfonate additives: SB-3 and DP-4. Additive SB-3 (barium sulfonate) is a barium salt of sulfonic acids obtained by selective purification of diesel oil. Additive DP-4 is a concentrate of oil-soluble calcium sulfonates obtained on the basis of heavy oil distillate.

 In the proposed method, alkaline earth metal sulfonates can also be used as part of marketable petroleum products, for example, as part of motor oils (GOST 17479-72) used to lubricate internal combustion engines. Of these, “D” group oils are most preferred (for example, M-8D, M-10D, M-20D, etc.) containing up to 20% sulfonate additives.

 Given the high cost and scarcity of all types of motor oils in the proposed method, oil products of the IMO group can be used as a carrier of oil-soluble sulfonates (used motor oils in accordance with GOST 21046-86) containing an increased percentage of sulfonate additives.

 Using the proposed method will provide the greatest effect in the flotation method of enrichment of “refractory” materials, characterized by an increased content of fine sludge, as well as in the flotation of coarse polymineral aggregates and large grains of recoverable minerals. Objects of this kind are intermediate products of the chemical enrichment of ferronickyl pyrrhotines when polysulfide-thiosulfate precipitator is used in the pulp preparation cycle, complex fayalite and calcium ferrite-slags of pyrometallurgical aggregates, refractory finely disseminated easily-sludge noble metals, sulphide-molybdenum ore sulphide-molybdenum-sulphide ore sulphides materials.

 Information on the use of petroleum oil-soluble sulfonic acids and / or petroleum oil-soluble alkaline earth metal sulfonates in the process of flotation of heavy non-ferrous metal sulfides in the study of patent and scientific literature has not been identified.

 The method is as follows.

 The initial polymetallic iron-containing material is subjected to preliminary preparation for flotation concentration. The essence of the preparation depends on many conditions: the characteristics of the genesis and chemical and mineralogical composition of the feedstock, the texture and structural features, the proximity of the flotation properties of the separated minerals, the degree of oxidation, strength, isomorphism, the ratio of useful components, the nature of the accompanying rock, etc. minerals are discussed in detail in specific examples. A sulfhydryl collector and oil-soluble sulfonic acids and / or their oil-soluble salts of alkaline earth metals are introduced into the pulp prepared for flotation. As a sulfhydryl collector, various xanthates (butyl, amyl, hexyl, isobutyl, isopropyl) aeroflot (dialkyl or diaryldithiphosphates) and their various combinations can be used. Due to the fact that oil-soluble sulfo compounds and products containing them are characterized by a high viscosity index, the proposed method provides for preliminary mixing of sulfonic compounds (acids of alkaline earth salts) with organic diluents. As diluents, low-boiling oil distillates (gasoline, kerosene, diesel fuel), natural gas condensate and products of its distillation, as well as mixtures of distillate and residual oil products, for example, motor and liquid fuel boiler fuels, can be used. The choice of diluent is determined by the specific conditions of the enrichment process and its availability. Sulfo compounds, their mixtures with a diluent, as well as sulfonated oil products are used in the form of aqueous emulsions, which greatly enhances the effectiveness of their collective action. The flow rate of the oil-soluble sulfo compounds and sulfhydryl collector introduced into the pulp corresponds to the mass ratio (0.005 0.10) 1, respectively. Depending on the characteristics of flotation, the supply of sulfo compounds from the sulfhydryl collector can be concentrated and fractional, simultaneous (including joint or separate) and alternate. If there is material in the pulp preparation sector for flotation, the stages of wet grinding of sulfonic compounds are mainly introduced into the pulp at this stage. The pulp treated with reagents is sent to flotation, during which valuable metals are introduced into the foam product as a collective polymetallic sulfide concentrate processed by known methods to produce salable metals and associated sulfur-containing products. The number of collector reagents introduced into the pulp in each case is selected experimentally, focusing on the quality of the resulting collective concentrate and tailings.

 Flotation products collective sulfide concentrate and tails are subjected to volumetric and weight measurements and analyzed. Based on the results of analyzes and measurements, the material balance of the process is calculated.

 Example 1 (experiment 1 table). The collective flotation method was carried out in laboratory conditions during the chemical enrichment of industrial pyrrhotite concentrate (PC), formed during the processing of sulfide copper-nickel ores of Talnakh and Oktyabrsky deposits of Norilsk MMC.

 Thin intergrowth of minerals in PC makes it impossible to separate them by traditional methods of mechanical enrichment.

 Nickel-containing PCs are processed using chemical enrichment technology, which is based on the autoclave oxidation of pyrrhotite in an aqueous pulp with oxygen to convert the bulk of sulfur to elemental, and iron to hydrated sulfates. Part of the heavy non-ferrous and platinum metals contained in the PC goes into solution. After the autoclave treatment of PCs, valuable metals are precipitated from an oxidized pulp solution in the form of secondary easily floated sulfides using metal iron or polysulfide-thiosulfate solutions as a precipitating agent. The autoclave pyrrhotite oxidation and precipitation operations comprise the field of pulp preparation of nickel-containing pyrrhotite materials for flotation separation of heavy non-ferrous and noble metals from iron and gangue components.

 After the deposition of valuable metals, the pulp is conditioned with petroleum oil-soluble sulfonic compounds (“red” sulfonic acids and / or alkaline earth metal sulfonates) and sulfhydryl collector in their mass ratio (0.005 0.10) 1, respectively. After this, the pulp is subjected to collective flotation, in which the sulfides of valuable metals and elemental sulfur are removed into the foam product collective sulfide concentrate containing also elemental sulfur, and oxide iron and rock in dump iron-tailings.

 Almost all waste rock and 80-90% iron are removed with the tailings of collective flotation. Due to the release of iron and rock-forming tailings, the mass fraction of valuable metals in the collective sulfide concentrate increases 2.5-4 times depending on the composition of the initial PC.

Collective sulfur-sulfide flotation is carried out at pH 4.5 from sulfate solutions containing 20 30 g / dm ³ iron and 0.1 0.3 g / dm ³ nickel. The complexity of flotation enrichment lies in the fact that ≈ 50% of the material supplied to the flotation is represented by particles of 5–7 μm, of which half are finely divided iron hydroxides. Another factor complicating the process of separation of minerals is the presence in the pulp of partially corroded grains of primary sulfides, which are characterized by low flotation activity, and large sulfur-sulfide aggregates that exceed the upper limit of flotation, which meets the conditions of the standard reagent mode.

 Flotation enrichment of nickel-containing pyrrhotite material was studied in a laboratory setup according to the scheme, including autoclave oxidation of pyrrhotite, precipitation of valuable metal sulfides, conditioning pulp with a collector, flotation separation of collective polymetallic concentrate.

As the starting material used "ordinary" pyrrhotite concentrate composition, Nickel 2.17; copper 0.64; cobalt 0.098; iron 49.19; sulfur 28.10; breed-containing 14.52, including SiO ₂ 8.51; CaO 2.15; MgO 1.39; Al ₂ O ₃ 2.47.

Pyrrhotite concentrate with a particle size of 80% minus 44 μm in the form of a water pulp with a ratio of Ж Т 1.55 was subjected to an autoclave oxidation treatment carried out in a titanium autoclave with a capacity of 3.0 dm ³ equipped with temperature and pressure control systems. For oxidation used industrial oxygen. The treatment was carried out at 150 ^o C and an oxygen pressure of 0.9 MPa in the presence of a surfactant, preventing wetting of the sulfide by molten sulfur. Processing time 40 min. Precipitation of precious metals from a solution of oxidized pulp was carried out by crushed metallized iron pellets at 95 ^o C for 30 min to a residual nickel concentration in the solution of 0.25 g / DM ³ .

The concentrate modified by oxidative treatment and precipitation in the form of an aqueous pulp with a ratio of W: T-1.5 was conditioned in a laboratory flotation machine with a chamber volume of 1 dm ³ . A sample of the pulp, taken at a rate of 350 g on a solid basis, was diluted in the chamber with water to W: T = 3 and, with the impeller turned on (without aeration), oil-soluble sulfonic acids and potassium butyl xanthate (BC) were introduced into the pulp in a ratio of 0.05: 1, respectively . The reagent consumption in terms of solid pulp was, g / t: sulfonic acid 5.0; xanthate 100.0. Sulfonic acids were pre-mixed with a diluent in a ratio of 1 to 20 and introduced into the pulp in the form of an aqueous emulsion. As a diluent, gas condensate diesel fuel of the FRG brand was used. Xanthate was used as a 5% solution. The duration of the conditioned pulp with reagents was 5 minutes

Collective flotation was carried out in a closed cycle on the principle of a continuous process. The material in the solid supply flotation contained nickel 1.85 1.87; copper 0.55 0.57; cobalt 0.08 0.085; iron 41.0 41.4; total sulfur 23.4 23.7, including elemental sulfur 16.5 16.7. The process scheme included the main control flotation and three cleanings of the foam product of the main flotation. The duration of the individual stages of flotation was, min:
Basic + control flotation 10
I cleaning 6
II cleanup 4
III cleanup 3
The efficiency of the reagent flotation regime was evaluated by the chemical composition of the products obtained, the level of extraction of valuable metals in the collective concentrate, and the consumption of sulfhydryl collector.

The oil-soluble sulfonic acids (NMS) used in the experiment were obtained by a known method (Schekhter Yu. N. Krein S... Teterina L. N. Oil-soluble surfactants. M. Chemistry, 1978, p. 96 116) by sulfonation of diesel oil M-11 gaseous sulfur trioxide. For sulfonation, industrial contact gas of the Norilsk MMC copper plant was used, containing, vol. SO ₃ 4 5; SO ₂ 0.5 0.6; O ₂ 10-15; the rest is nitrogen.

 The results of the experiment are presented in the table. The combination of petroleum oil-soluble sulfonic acids with butyl xanthate with a mass ratio of 0.05 1 provided a high level for the extraction of non-ferrous and noble metals, nickel 94.5; copper 89.4; cobalt 94.2; platinum 86.2; palladium 83.3; rhodium 72.4; ruthenium 58.2; gold 79.1; silver 68.3. Collective flotation concentrate in the total contained 7.03% heavy non-ferrous with a mass ratio of iron to the sum of heavy non-ferrous metals 3.50.

 Example 2 (experiment 2 tables). The pyrrhotite concentrate used, the equipment and material enrichment conditions are the same as in Example 1. The difference is that barium sulfonate extract was used as the oil-soluble sulfonic acid compound, which was used in combination with butyl aeroflot (BA) at a mass ratio of these reagents of 0.005 : 1 respectively.

 The extract of oil-soluble barium sulfonates was isolated from the SB-3 grade sulfonate additive (GOST 10534-78) by chromatographic method. The work was carried out according to the standard method used for analysis in the sulfonate additives of the mass fraction of the active substance (Clause 3, GOST 10534-78 "Sulfonate additive SB-3". The calculated amount of the obtained extract (mass fraction of the active substance ≈ 90%) was mixed with a diluent FGD gas condensate diesel fuel in a ratio of 1:20, respectively. The mixture was emulsified in the presence of butyl aeroflot. Collector reagents in the form of a joint emulsion were fed into the conditioning process. Oil-soluble barium sulfonates were introduced amount of 0.5 g, and butyl aerofloat in an amount of 100 g per 1 ton of solids in the flotation nutrition.

 The extraction of valuable metals in the collective concentrate amounted to Nickel 92.6; copper 87.1; cobalt 92.0; platinum 84.7; palladium 85.1; rhodium 71.1; ruthenium 56.7; gold 77.2; silver 65.9. The total content in the concentrate of heavy non-ferrous metals is 6.905%. The mass ratio of iron in concentrate to the sum of heavy non-ferrous metals is 3.58.

 Example 3 (experiment 3 tables). The initial pyrrhotite concentrate, equipment and conditions of flotation concentration of the material are the same as in example 1.

 The only difference is that calcium sulfonates were used as the oil-soluble sulfo compound in the detergent-dispersing sulfonate additive of the DP-4 brand (TU 0257-003-13230476-94 (mass fraction of the active substance 30%). The consumption of the additive was 33.3 g which corresponded to a consumption of calcium sulfonates of 10 g / t of solid pulp. A selected aliquot of the additive was mixed with a diluent (diesel fuel RGD) in a ratio of 1:20 and a 5% aqueous emulsion was prepared from the mixture. Butyl xanthate was used as a collector with a flow rate ohm 100 g / t. The reagents were introduced into the pulp in turn: initially xanthate and only after 2 minutes the emulsion of the additive DP-4. The mass ratio of calcium sulfonates and xanthate was 0.1: 1.

 In this experiment, a collective flotation concentrate was obtained with a total content of heavy non-ferrous metals of 6.96% and a mass ratio of iron to the sum of heavy non-ferrous metals of 3.53. The concentrate recovered, nickel 95.1; copper 91.7; cobalt 94.9; platinum 87.4 palladium 84.6; rhodium 74.2; ruthenium 60.5; gold 82.0; silver 71.3.

 Example 4 (experiment 6 of the table). The experimental conditions, including the initial pyrrhotite concentrate, equipment, pulp preparation mode of the material, and collective flotation mode are the same as in example 1.

 The difference lies in the fact that sulfonic acids obtained by treating DT motor fuel according to GOST 1667-68 (molecular weight 450 cu) with contact gas were used as the oil-soluble sulfo compounds. The method of sulfonation of motor fuel, the equipment and composition of the contact gas are similar to those described in Example 1. The mass ratio of sulfonating agent in terms of sulfur trioxide to the processed product was 1: 25. The obtained sulfonic acids were introduced into the conditioning process as a part of sulfonated motor fuel (mass fraction of active substance 20% ). The product, taken in an amount of 20 g (based on 5 g of sulfonic acids per 1 ton of solid pulp), was pre-mixed with diluent DGD diesel fuel in a ratio of 1:10, after which the mixture was emulsified and added to the treated pulp. 2 minutes after the addition of sulfonic acids, butyl xanthate was introduced into the pulp in an amount of 100 g / t solid pulp. The mass ratio of the dosed oil-soluble sulfonic acids and xanthate in this example was 0.05: 1.

 During flotation of the modified pyrrhotite material into the collective concentrate, nickel was recovered, 94.2; copper 89.5; cobalt 93.9; platinum 86.0; palladium 83.2; rhodium 72.6; ruthenium 57.9; gold 78.8; silver 68.4. The concentrate contained heavy non-ferrous metals 7.12% mass ratio of iron to the amount of non-ferrous metals 3.47.

 Example 5 (experiment 8 of the table). The experimental conditions are the same as in Example 1. The difference is that a mixture of oil-soluble calcium-barium sulfonates introduced as part of the spent oil product of the MMO group GOST 21046-86 (mass fraction of oil-soluble sulfonates is 12%) was used as the sulfo compound. The spent oil in an amount of 41.7 g / t of solid pulp (5 g / t of oil-soluble sulfonates) was mixed with kerosene diluent in a ratio of 1: 5 and the mixture was emulsified. The emulsion was prepared on a 5% solution of butyl aeroflot, used in this experiment as a sulfhydryl reagent collector. Aeroflot consumption was 100 g / t of solid pulp, the mass ratio of sulfonates and aeroflot was 0.05: 1. The emulsion mixture was introduced into the pulp, conditioning and collective flotation were performed.

 Extraction of valuable metals into the collective concentrate was, nickel 94.0; copper 88.7; cobalt 93.8; platinum 85.7; palladium 83.1; rhodium 69.8; ruthenium 57.6; gold 79.0; silver 67.5. The concentrate contained 6.677% of the total amount of heavy non-ferrous metals, the mass ratio of iron to the sum of heavy non-ferrous metals is 3.65.

 Based on the experiments performed at different ratios of oil-soluble oil sulfonic compounds and sulfhydryl collector, it is seen that the ratio (0.005 - 0.10) 1 is optimal for collective flotation of sulfides. Moreover, the sequence of supply of sulfo compounds and sulfhydryl collector does not significantly affect the flotation result.

 For a comparative assessment of the effectiveness of the proposed method, experiments were carried out to enrich the pyrrhotite concentrate in the prototype method mode. The experiments were carried out under conditions identical to the conditions of example 1. In this case, a collective concentrate was obtained containing 6.24% of the sum of non-ferrous metals with a mass ratio of iron to the sum of non-ferrous metals of 3.78. Extraction of valuable metals in the concentrate amounted to 88.9 nickel; copper 85.8; cobalt 88.2; platinum 74.1; palladium 71.3; rhodium 5.96; ruthenium 47.4; gold 65.3; silver 54.6. Sulfhydryl collector in the prototype method of the user with a flow rate of 250 g / t

 A comparison of the results shows that the collective flotation of the modified pyrrhotite concentrate according to the proposed method proceeds more efficiently than in the known prototype method.

 Single experiments conducted with a combination of diluent and sulfhydryl collector (without the addition of oil-soluble sulfonamide) showed lower results than in the experiments according to the prototype method. This indicates an insignificant inherent effect of the diluent of sulfonic compounds on the indicators of collective flotation.

 Example 6 (experiment 9 of the table).

 Studies were performed on a porphyry-type sulfide copper-molybdenum ore sample containing molybdenum 0.0087; copper 0.55; iron 5.01; sulfur 4.52. Molybdenum in the ore was in the form of molybdenite, which formed rather large precipitates and disseminated in quartz (approximately 70% of molybdenite had a flake size of 0.5 to 0.1 mm). Ore minerals in the sample were present in the form of inclusions, blotches and films. Prevailed, pyrite 7.1; chalcopyrite 1.6 and hematite 1.5; Bornite and covellins were also present, the number of which did not exceed fractions of a percent. Chalkosin and magnetite were found in the form of rare single grains. The bulk of chalcopyrite was represented by individual grains (0.01 0.3 mm) or clusters associated with pyrite and molybdenite. Gold and silver, which are characteristic elements of copper-molybdenum ores, were mainly present in the form of submicroscopic inclusions of their own minerals (native gold, petcite, argentite, etc.) in sulfide minerals chalcopyrite and pyrite. The host rock was mainly represented by quartz 45 and feldspar 27; a significant amount of 6.8 contained biotite, and less than 2.1 carbonates (calcite, siderite).

 A portion of the initial ore with a grain size of 2.0 mm was crushed in a laboratory ball mill to a particle size of 40% of the class minus 74 μm with a grade of plus 150 μm ≈ 37%. The coarse grinding of the ore was determined based on its structural and texture features and at the same time aimed at a more complete identification of technological the possibilities of the proposed method. The practice of enrichment of porphyry copper-molybdenum ores shows that coarse grinding of ore material can reduce the degree of sludge molybdenum softer than the main minerals of the host rocks, and thereby reduce the loss of molybdenum in the form of thin slags. In this regard, coarse grinding is preferable for collective flotation of molybdenum ores (A. Abramov. Technology for the processing of non-ferrous metal ores. M. Nedra, 1983, p. 157 169). At the same time, underfinished ore contains large velocities of ore minerals (molybdenum, chalcopyrite, etc.) with quartz and feldspar, the flotation of which under standard reagent conditions is quite difficult due to the low flotation activity. Mineralogical analysis showed that the selected degree of grinding fineness provided a sufficient completeness of opening of ore grains: already in the class of 300 150 μm, molybdenite was predominantly represented by open splices with quartz and partially free grains, which under suitable conditions could be swallowed. Closed splices were quite rare. Pyrite and chalcopyrite in the large class were also present in large intergrowths with quartz and feldspar, the size of which was mainly in the range of 40 to 100 μm.

 The grinding of the initial ore was carried out at a ratio of T: W: W = 1: 0.7: 6. Two minutes before the end of grinding, an emulsion of a sulfonate additive of the brand DP-4 (TU-0257-003-13230476-94) with a mass fraction of the active substance of 30% was added to the mill. The additive was mixed with the diluent with DT motor fuel at a mass ratio of 1 before preparation of the emulsion : 10 respectively. Additive consumption was 4 g / t of ore, diluent (motor fuel) 40 g / t.

 The laboratory flotation laboratory design included the main and control collective flotations to produce rough copper-molybdenum concentrate and tailings.

 In the main flotation, potassium butyl xanthate (15 g / t), T-80 blowing agent (50 g / t) were used as sulfhydryl collector. The duration of the main collective flotation of 10 minutes

 The consumption of collectors in the control collective flotation cycle was as follows, g / t: sulfonate additive (DP-4) 2.7; motor fuel (diluent) 27; potassium butyl xanthate 10. Foaming agent consumption 20 g / t. The duration of the control flotation was 15 minutes

 Concentrates of the main and control flotation operations were combined into a collective copper-molybdenum product. In both flotation cycles, the mass ratio of oil-soluble sulfonates to butyl xanthate was 0.08: 1.

 The efficiency of the process was evaluated by the extraction of valuable metals in a collective copper-molybdenum product and the degree of enrichment of the concentrate for non-ferrous metals relative to their content in the original ore.

 For a comparative assessment of the effectiveness of the proposed method in analog conditions, experiments were carried out in prototype modes, the closest analogues and with the independent use of a diluent (motor fuel).

 Obtained by the proposed method, the draft collective copper-molybdenum concentrate contained, molybdenum 0.0864; copper 5.21. Extraction of metals in concentrate, molybdenum 93.4; copper 89.1; gold 91.5; silver 91.8. The degree of enrichment of the concentrate in molybdenum and copper relative to the original ore ≈ 9.9.

 A comparison of the research results shows that the use of the proposed method for the enrichment of copper-molybdenum sulfide ores in comparison with the prototype allows to increase the extraction of rough copper-molybdenum concentrate of molybdenum by 5.2% copper by 7.1% gold by 5.6% silver on 5.7% while maintaining the quality of the concentrate by the content of valuable metals and at the same time reducing the total consumption of xanthate ≈ 15% rel.

 In addition, it was found that the combined use of a sulfhydryl collector and an oil-soluble sulfo compound in a collective copper-molybdenum flotation cycle allows coarsening of ore grinding without reducing the enrichment process. The developed reagent mode provided the same extraction of valuable metals in the collective concentrate during grinding 40% minus 74 microns, as in the standard factory mode, when grinding 55 60% minus 74 microns. This provides important technological, economic and operational advantages: it increases the productivity of grinding equipment and reduces energy consumption for ore pulp preparation, reduces sludge formation, reduces the duration and front of main flotation flotation machines, allows for more granular and denser tails that require smaller areas for thickening and more favorable for storage .

 Example 7 (experiment 10 of the table).

 Iron-silicate (fayalitic) slag of sulphide raw material smelting in suspension was obtained by flotation enrichment, obtained by processing complex copper concentrate containing nickel, cobalt and platinum group metals.

Due to the high content of valuable metals, slag from suspended smelting furnaces is not dumped. In world industrial practice, two methods of depletion are used:
flotation of sulfide from pulp of crushed slag;
electric furnace method.

 An important advantage of the flotation concentration method is the relatively low energy consumption, simplicity of hardware design and moderate operating costs. However, at present, this method is used very limitedly and only for the processing of slag suspended smelting pure copper concentrate. The latter is due to the unsatisfactory recovery of transition and platinum metals into the foam product during flotation of slag from the processing of complex sulfide raw materials. (Sinev L.A. Borbat V.F., Kozyura A.I. Smelting of sulphide concentrates in suspension. M. Metallurgy, 1979, p. 125 127).

In the present experiment, iron-silicate slag of suspended smelting containing 0.34 nickel was used; copper 1.41; cobalt 0.055; iron 40.35. The silicate part of the slag had a composition of SiO ₂ 34.53; CaO 2.42; MgO 1.15; Al ₂ O ₃ 4.87.

The studies were carried out on slags prepared according to the method of Outokumpu (Finland), according to which liquid slag was cooled in 600 mm thick molds for 10 hours. The ingot obtained was further cooled by irrigation with water, crushed to a particle size of 2 mm and ground in a laboratory ball mill to 96 % grade minus 44 microns. A portion of the ground slag was adjusted with water to a density of 1.28 kg / dm ³ , conditioned with reagents, and floated in a laboratory flotation machine with a capacity of 1.5 dm ³ . Flotation was carried out in a neutral medium (pH 6.5) in the presence of two collector reagents: isopropyl xanthate (150 g / t) and calcium sulfonate additive DP-4 TU 0257-13230446-94 (45 g / t). Additive DP-4 (wt.% Active substance 30%) was previously dissolved in DT grade motor fuel (1:10) and emulsified. Collectors were injected into the pulp in turn: first, the emulsion DP-4, then a solution of xanthate. The mass ratio of calcium sulfonates and xanthate was 0.09: 1. As a foaming agent, T-80 was used in an amount of 65 g / t. Duration of flotation 30 minutes

 Flotation products of sulfide copper concentrate and tails were subjected to volumetric weight measurements and analyzed. Based on the results of analyzes and measurements, the material balance of the process was calculated.

 The experimental results indicate the high efficiency of the proposed method. Despite the fact that fayalitic slag, crushed to a finely dispersed state, is difficult to enrich, the flotation process was characterized by sufficient complexity of the target extraction of all valuable metals. The completeness of metal extraction in concentrates was, nickel 78.2; copper 93.5; cobalt 65.6; platinum 94.1; palladium 92.7; rhodium 82.7; ruthenium 77.2; gold 95.3; silver 94.6. The resulting copper concentrate (yield 8.8%) contains 20.53% of the amount of non-ferrous metals and 39.8% of iron, which corresponded to a concentration of 10.2 with respect to the initial fayalitic slag.

 In comparison experiments conducted in the mode of the prototype method, and when flotation with one sulfhydryl collector (isopropyl xanthate), the recovery rates of metal securities and the quality of the flotation concentrate were noticeably lower than in the proposed method.

 Extraction of valuable metals in copper concentrate in the prototype method amounted to nickel 71.4; copper 90.2; cobalt 52.1; platinum 82.4; palladium 79.3; rhodium 71.4; ruthenium 64.9; gold 89.1; silver 87.5. The resulting flotation concentrate contained 17.61% of the total non-ferrous metals (concentration 8.8), and the optimal consumption of isopropyl xanthate corresponded to 220 - 250 g / t of slag.

When flotation of slag with one isopropyl xanthate (consumption 350 g / t), satisfactory results of the complexity of the extraction of valuable metals were not achieved. Nickel and cobalt recovery in concentration was only 56.4 and 38.7%, respectively, and the loss of platinum group metals with flotation tails was at the level of 33.5 41.2%
Thus, when flotation enrichment of slag suspended smelting, the proposed method compared with the prototype allows to increase the extraction in the collective concentrate of non-ferrous metals by 3.3 13.5% of platinum group metals by 11.3 12.3% of gold by 6.2% silver per 7.1% At the same time, an average of 36.2% rel. reduced consumption of expensive sulfhydryl reagent-collector.

 Example 8 (experiment 11 of the table).

As the starting material used aqueous pulp (W: T = 3.5) of iron-hydrated tails of the technology of chemical enrichment of nickel-pyrrhotite concentrate, containing:
in solid, nickel 0.32; copper 0.21; cobalt 0.025; iron 49.2; total sulfur 8.3. including elemental sulfur 3.4;
in liquid, g / dm ³ : nickel 0.11; copper 0.005; cobalt 0.025; iron 10.2; cepa 6.7; noble metals traces.

 In solid iron hydrate tails, heavy non-ferrous metals are mainly in the form of ore sulfides (pentlandite, chalcopyrite, cubanite, etc.), represented by intergrowths with undegraded pyrrhotite, sulfur, and non-sulfide minerals. The surface of the intergrowths is covered with films of hydrated iron oxides, depressing their flotation and predetermining the transition of non-ferrous metals to dump tailings (Mantsevich M. I. Malinsky R. A. Shcherbakov V. A. et al. Non-ferrous metals. 1983, N 1, p. 77) .

 The forms of finding noble metals in iron hydrate tails are individual for each metal. In the case of plates and palladium, these are poorly floating sludges of their own minerals. The bulk of the rare platinum metals (RPMs) that have passed into the tails is formed by extracting them into solution during the destruction of the pyrrhotite crystal lattice and subsequent sorption on the constantly formed oxide phase with a developed surface. The bond between the sorbate and the sorbent in this case is chemical in nature and quite strong. Part of the pyrrhotite during autoclave leaching by the solid mechanism, which excludes the transition of iron into solution, and in this part of the material, the platinoids remain bound to the main (iron) via oxo-bridges, i.e. even more durable.

 The general formula for finding noble metals in tails is their associates with relict ore sulfides pyrrhotite, pentlandite, chalcopyrite (Radiation of the behavior of the platinum group metals in the processing of pyrrhotite concentrates // Scientific and Research Report of the Moscow Institute of Chemical Technology and Technology / Development of scientific fundamentals and verification of technological processes, providing an increase in the recovery of platinum group metals at Norilsk Mining and Metallurgical Complex, N GP 8175925, M. 1982, p. 49 51).

 Preparation of the starting material for flotation extraction of valuable components included preliminary acid-reduction activating treatment of the tailings (ed. St. USSR N 832975, class C 22 B 3/00; 23/04; C 22 B 11/04 according to the application N 2870183 / 22-02 with a prior. From 14.01.80).

The pulp was processed in a laboratory reactor with a capacity of 1 dm ³ with mechanical stirring, equipped with systems for measuring and controlling pH and temperature. 0.9 dm ^{3 of the} pulp of the initial tailings were loaded into the reactor and heated to a temperature of 90 ± 5 ^° C. With stirring, aluminum was fed into the pulp in the form of a powder with a grain size of minus 150 μm, with a metal aluminum content of 95.6% (aluminum powder was obtained by grinding metal chips in a laboratory ball mill). From the moment of aluminum supply, the activation treatment time, which was 3 hours, was counted. During the treatment, the pH of the pulp was maintained at the level of 3.0 by applying a solution of sulfuric acid (1: 1) using an automatic titrator (BAT). The consumption of aluminum was 2 g per 1 g of the sum of non-ferrous metals in the initial pulp. This mode of processing iron hydrate tails is optimal for subsequent flotation extraction of heavy non-ferrous and platinum metals from them into a collective sulfide concentrate (ed. St. USSR N 832975).

At the end of the activating treatment, the pulp was cooled, conditioned with a blowing agent, collector reagents were introduced and flotated in a laboratory flotation machine with a chamber capacity of 1.5 dm ³ . Flotation was carried out in an open cycle for 15 min (10 min main and 5 min control). As a blowing agent, T-66 was used in an amount of 30 g / t solid feed pulp. The collector reagent was introduced into the pulp together in the form of an emulsion of barium sulfonates in a solution of butyl aeroflot. Barium sulfonates were introduced into the SB-3 sulfonate additive (GOST 10534-78), which was previously mixed with a diluent (FGD) in a ratio of 1:20. The specific consumption of collector reagents was: butyl aeroflot 50.0; sulfonate additives (wt.% active substance 12%) 20.8 g / t solid in flotation feed. The mass ratio of barium sulfonates and aeroflot was 0.05: 1.

 In flotation practice (pulps of sulfide concentrate and tailings) after separation and weight measurements, the content of heavy non-ferrous metals, platinum, iron and sulfur was analyzed.

 The resulting flotation concentrate (yield 3.3%) was characterized by the following composition, nickel 6.6; copper 4.7; cobalt 0.5; iron 26.4; sulfur 47.8. Extraction into a concentrate of heavy non-ferrous and precious metals amounted to 68.2 nickel; copper 73.1; cobalt 65.4; platinum 65.0; palladium 66.1; rhodium 51.3; ruthenium 40.2; gold 62.8; silver 60.3.

 For comparison, under the same conditions, experiments were carried out on flotation concentration of iron-hydrated tailings using the reagent mode according to the prototype method. The obtained technological indices of completeness of tailings enrichment in this case are significantly lower, despite the higher consumption of sulfhydryl collector (100 g / t solid feed pulp). With the same quality of the flotation concentrate (the ratio of iron to the sum of non-ferrous metals 2.31), the completeness of extraction of valuable metals into the foam product was 55.4% for nickel; copper 63.5; cobalt 50.7; platinum 48.1; palladium 52.9; rhodium 41.8; ruthenium 33.7; gold 53.6; silver 49.2.

 Thus, the use of the proposed method for the enrichment of iron-tailings containing sulfides of heavy non-ferrous metals and minerals of noble metals, compared with the prototype allows to increase the extraction of non-ferrous metals by 9.6 14.7% of platinum group metals by 6.5 16.9% of gold by 9.9% silver by 11.1% At the same time, the consumption of sulfhydryl collector is reduced by 50% without reducing the quality of the resulting concentrate.

 The table shows examples that differ in the type of oil-soluble oil-soluble sulfonic compounds and products containing them, as well as the ratio of sulfonic compounds and sulfhydryl collector.

 According to the obtained experimental results (experiments 1 3, 6 11), the proposed method provides high recovery of heavy non-ferrous and noble metals in a collective sulfide concentrate regardless of the nature of the processed complex ferrous raw materials and the type of sulfhydryl collector used. At the same time, the quality of the collective concentrate is improved and the consumption of the sulfhydryl reagent-collector is reduced.

 The results of experiments 9 and 10 indicate the high efficiency and versatility of the proposed method for the enrichment of hard-to-float materials, characterized by an increased content of particles of the maximum fineness of fine sludge (op.10) and large aggregates (op.9).

 A comparison of the results of experiments 3.6 11 with the results of experiments 1 and 2 of the table shows that petroleum oil-soluble sulfo compounds work equally efficiently as part of marketable petroleum products (motor oils, detergent-dispersant additives, sulfonated fuels), and in a free state in the form of concentrated extracts "red" sulfonic acids and alkaline earth metal sulfonates.

 From the point of view of the economics of the flotation process and the provision of consistently high technological results, the most rational is the use of sulfonate detergent-dispersant additives, which are distinguished by their availability, manufacturability and stability of the material composition. As diluents, it is preferable to use gas condensate and petroleum distillates or mixtures thereof.

Claims (3)

 1. A method for collective flotation of sulfides containing noble metals from polymetallic iron-containing materials, including preliminary preparation of the material for flotation, introducing an oil-soluble oil-soluble sulfur-containing reagent and a sulfhydryl collector into the pulp and recovering valuable metals into a foam product — a collective sulfide concentrate, characterized in that sulphonic acids and / or their salts are used as oil-soluble oil-soluble sulfur-containing reagent grinding metals in a mass ratio with sulfhydryl collector (0.005 0.10) 1, respectively.  2. The method according to claim 1, characterized in that the petroleum-based oil-soluble alkaline earth metal sulfonates are used in the form of detergent-dispersant additives to base lubricating oils or as part of marketable petroleum products containing them.  3. The method according to claim 1, characterized in that the petroleum-organic oil-soluble alkaline earth metal sulfonates are used in the composition of used automobile oils.

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