A method of processing material serosorting

 

(57) Abstract:

The invention relates to the field of hydrometallurgy, in particular to a method of processing serosorting material released by sulfuric acid autoclave-oxidative leaching of sulfide raw materials, obtaining sulfur and sulfide concentrates sent to further processing. The method includes processing the aqueous pulp material calcium reagent-hydrophilization (lime, sulphide of calcium, nepheline sludge, Portland cement clinker) in the presence of organic surfactants such as higher fatty alcohols, oil adsorption resins, vegetable oils, etc. at a temperature above the melting point of elemental sulfur with a mixture containing svezheosazhdennoi calcium sulfate and elemental sulfur, followed by cooling and flotation pulp with obtaining sulfur and sulfide concentrates. When this mass ratio svezheosazhdennoi calcium sulfate and elemental sulfur added in the mixture is 1 : (8 - 100), and its consumption is equal to 1 to 25% by weight serosorting material. As a mixture containing svezheosazhdennoi calcium sulfate and elemental sulfur, can be apollotheatre, to improve the content of elemental sulfur in a sulfur concentrate to 80.6 and 88.5%, while its content in sulphide concentrate on the level of 2.1% to 3.8% and in the terms of use widely available calcium reagent-water-wetting agents repeatedly to reduce the consumption of hydrocarbon organodetrital organic surfactants. 1 C.p. f-crystals, 1 table.

The invention relates to hydrometallurgy, in particular to a method of processing serosorting material released by sulfuric acid autoclave-oxidative leaching of sulfide raw materials, obtaining sulfur and sulfide concentrates sent to further processing.

A method of refining serosorting material with obtaining sulfur and sulfide concentrates, including water treatment pulp material reagent-hydrophilization at a temperature that ensures the melting of sulfur, preferably at 120-130aboutC, cooling the treated pulp and subsequent flotation, in which the reagent-hydrophilization use these alkaline compounds: sulfur hydroxide, caustic soda, lime, or a mixture thereof.

The disadvantage of this method is that the application as R is the cost of processing serosorting material, as these salts are expensive and in short supply. In addition, the sodium disposal of wastewater generated in processing technology serosurvey materials, complex and requires a high cost. Lime, in comparison with salts of alkali metals, is more affordable hydrophilization. However, its use makes the process stabilizers sulfuric emulsion, such as calcium carbonate (lime admixture) and calcium sulfate formed by the interaction of hydrophilization with sulfate ions present in the pulp is processed serosorting material. Stabilizers prevent coalescence of droplets of sulfur during processing, making their re-formation in collisions, and thereby reduce the degree of separation of sulfur and sulfides, i.e., the efficiency of the operation. Eventually deteriorating the selectivity of the subsequent flotation and as a consequence decreases the quality of the obtained sulfur and sulfide concentrates. The bulk of the sulphur in the sulphur concentrate (70-90%) is represented by a class size of minus 44 microns. Subsequent melting of this fine material is highly unstable.

A method of refining serosorting material including the disintegration of the pulp of satara, in which to reduce the negative effects of stabilizers sulfuric emulsion, the disintegration add organic surface-active substance (surfactant).

Addition of organic surfactant contributes to the escalation of droplets of sulfur by improving the conditions of their coalescence and increases the selectivity of the subsequent flotation. However, the effectiveness of these reagents as destabilization sulfur emulsions are insufficient for sustainable production of high-quality concentrates sulphur content of elemental sulfur at least 80% when its content in sulphide concentrate not more than 4% and, accordingly, does not provide high technical and economic indicators of their processing. Autoclave smelting of sulfur from concentrates with low content of elemental sulfur (below 80%) when using calcium reagent-water-wetting agents is complicated by the formation of multiple emulsions (so-called "heads"), which reduces the release of sulfur and greatly increases the cost of processing the received tails. The high content of elemental sulfur in the sulfide concentrate considerably complicates the pyrometallurgical processing of concentrate causes the formation wall accretions in the drying units, leads the ri smelting sulphide concentrate the contained sulfur is oxidized to form sulfur dioxide. Therefore, the increase in the content of sulfur in the sulfide concentrate, besides the fact that it is associated with high losses, it is desirable also from an environmental point of view - the additional amount of elemental sulfur deposited on the heat, increases the release of sulfur dioxide, which in turn increases the amount of waste metallurgical gases and increases air pollution environmentally hazardous sulfur compounds.

Also known organic surfactants used in processing technology serosorting material themselves have negative side properties inherent in the nature of these compounds, in particular, pinagsama properties VIS have a negative impact on the flotation process, and hydrocarbons that form the basis of Nefteugansk surfactants reduce the grade sulfur, causing the need for additional purification from organic impurities.

The problem solved by the invention is the development of a method for processing serosorting material providing sulfur and sulfide concentrates superior quality cstavlenna task is solved by in a known method of obtaining sulfur and sulfide concentrates from serosorting material, including water treatment pulp material calcium reagent-hydrophilization in the presence of organic surfactants at a temperature above the melting point of elemental sulfur, cooling the slurry and subsequent flotation of obtaining sulfur and sulfide concentrates according to the invention the treatment is carried out with addition of a mixture containing svezheosazhdennoi calcium sulfate and elemental sulfur at a mass ratio of 1:(8-100), respectively, in the amount of 1-25% by weight serosorting material.

Another difference of this method is the use as an add mixture of the obtained sulfur concentrate.

In the development process of the proposed method, it was found that svezheosazhdennoi calcium sulfate introduced into the pulp serosorting material in the mixture with elemental sulfur at a specific ratio of ingredients, despite the increase in the total content of calcium sulfate in getintegervalue pulp, effectively contributes to the destabilization of sulfuric emulsion due to the formation of compact coarse sediment guy who I am. While it is preferable to add a mixture of calcium sulfate had an active surface, i.e., was "freshly prepared", which can be achieved, for example, the return part of the sulphur concentrate obtained in the processing serosorting material. Thus, according to the invention an additional amount of calcium sulfate introduced into the mix of the proposed composition, performs the function of desactivate the surface of the gypsum formed in getintegervalue the pulp resulting from the interaction of calcium reagent-hydrophilization with components of the liquid phase. By suppressing the stabilizing effects of gypsum phase on the process of coalescence of the droplets of sulfur increases the efficiency of organic surfactants, which can significantly reduce its consumption by disintegration without deterioration process.

However, it is established that independent additive svezheosazhdennoi calcium sulfate is ineffective, because by its dilution serosorting material reduces the selectivity of the subsequent sulfuric flotation. To eliminate the factor of dilution calcium sulfate is injected into the slurry in a mixture with elemental gray is Oh sulfur added in the mixture should not exceed 1:8 (at least 8 hours sulfur). At higher value of this parameter is the quality of the obtained concentrates on the content of elemental sulfur is lower than in the prototype. The optimum ratio svezheosazhdennoi calcium sulfate and elemental sulfur(1:8) - (1: 100), and the amount of addition of the mixture should be 1-25% by weight serosorting material. Outside this range the results of the use of the method is significantly reduced: at a flow rate of the mixture is less than 1% sulphur concentrates contain only 71,4% of elemental sulfur, while its content in sulphide concentrate is 7.6% (i.e., approximately 1.5 times higher than the regulated limit); an increase in the consumption of a mixture of more than 25% is impractical for environmental reasons, but also because of the deterioration process.

As a mixture containing svezheosazhdennoi calcium sulfate and elemental sulfur, can be used part of the sulphur concentrate, derived from serosorting material with the use of calcium reagent-hydrophilization. The mass ratio CaSO4and Sothis product is the experience of MMC Norilsk is(1:15)-(1:80).

Most of the available calcium reagent-hydrophilization Sul is aniah - in the form of binary, ternary and more complex salts, for example, two - and tricalcium silicates ( - 2CaO SiO2and 3CaO SiO2respectively), in the composition of the technical product and process waste: air and hydraulic lime (anhydrous and hydrated forms), Portland cement clinkers (3CaO SiO2and - 2CaO SiO2), belitovogo sludge ( - 2CaO SiO2), product recovery phosphogypsum or natural anhydrite (CaS, CaO), as well as some industrial products in the production of alumina containing small amounts of aluminum and iron. Effective reagent - hydrophilization are calcium polysulfides, which are used in the form of polysulfide-thiosulfate solutions obtained by the hydrothermal interaction of alkaline calcium salts to elemental sulfur.

As organic surfactants when processing serosorting material, it is preferable to use oil containing in its structure the adsorption resin with the number of carbon atoms in the molecule 25-77. To the number of specified petroleum products include fuel oil, a mixture of tars and bitumens with distillate fuel, motor fuel for low-speed diesel engines, such as GOST 1667-68), industrial and transmission is erecti oils and fuels. In addition detergency as surfactants can be used vegetable oils, animal fats, polysiloxane fluid, higher fatty alcohols, carboxylic acids and their various compositions.

The method is as follows. In the pulp serosorting material obtained after sulfuric acid autoclave-oxidative leaching of sulfide raw materials, injected with a mixture containing svezheosazhdennoi calcium sulfate and elemental sulfur at a mass ratio of components(1: 8) - (1:100) accordingly, in the amount of 1-25% by weight of source material. As the mixture can be used sulphur concentrate containing svezheosazhdennoi calcium sulfate and elemental sulfur in a ratio of 1:(15-80). The resulting suspension is treated in an autoclave at a temperature above the melting point of sulfur to calcium reagent-hydrophilization, for example lime, sulphide of calcium, lime-sulfur broth, nepheline (believes) sludge in the presence of organic surfactants. After processing is complete, the slurry is cooled and subjected to flotation for separation of elemental sulfur and ferrous metals in individual products - sulphur and sulphide concentrates. Of the sulphur concentrate known meta disintegration sulfur concentrate part of its return in this operation, The number added to the disintegration of sulfur concentrate in each case choose the experimentally depending on the quality of sulfur and sulfide concentrates. The total consumption of sulfur contained in the concentrate, calcium sulfate and elemental sulfur varies from 1-25% by weight of source material. The sulphide concentrate is sent to the pyrometallurgical production for commodity metals or their salts.

The proposed method is described in the specific examples and the results are shown in the table.

The experiments were conducted on an industrial pulp "ordinary" serosorting concentrate (SPC) obtained in autoclave technology oxidative leaching of pyrrhotite concentrate on the Norilsk mining and metallurgical combine.

The composition of the pulp SCQ solids, %: Nickel 6,72; copper 2,1; iron total 26,1, including iron oxide 16,9; sulfur total of 50.4, including elemental sulfur - 37,7; in solution, g/DM3: Nickel 0,13; copper 0,059; iron total 4,19; total sulfur 3,79; sulfate ion 10,1.

The pH of the pulp 4,7; W:t 1,45.

P R I m e R 1 (experiment 1 table). In the pulp serosorting concentrate (SPC) when displacement is the weight of the FCS in the mass mixing ratio of 1:55, respectively, freshly prepared precipitate calcium sulfate was obtained by neutralizing a solution of 2n. sulfuric acid calcium hydroxide to pH = 5. The residue was pre-agglomerated and mixed with elemental sulfur in a predetermined ratio. As elemental sulfur used crushed technical sulfur grade 9950 (GOST 127-76) size class 150+74 microns.

Suspension SCQ and seocalcitol mixture in an amount of 2.5 DM3were loaded into the autoclave with mechanical stirring with a capacity of 5 DM3heated "deaf" with steam. Here is sequentially added to the sulphide of calcium in the amount of 4.3% by weight of the FCS and organic surfactant - fuel oil brand 100 (GOST 10585-75) with a flow rate of 0.01% of the weight of the FCS. The slurry was heated to 130aboutC, was treated under stirring for 30 min, cooled and unloaded. The treated pulp was subjected sitonomy analysis classes 150 and 210 μm and fluoroware on laboratory photomachine capacity of the camera 1 DM3. The obtained products were weighed, were separated by filtering the solid and liquid phases were analyzed for the content of elemental sulfur and based on the results of the sieve and chemical analyses was calculated sulphur distribution by class size and its extraction by flotation in km amounted to 79.2%; this class contained 96.4% of elemental sulfur. The obtained sulfur and sulfide concentrates contained 86,2 and 2.3% of elemental sulfur, respectively. Removing elemental sulfur in a sulfur concentrate were $ 97.6%.

P R I m m e R 2 6 tables). Used pulp SSK, equipment and conditions of operation are the same as in example 1. The difference is that as mixtures containing svezheosazhdennoi calcium sulfate and elemental sulfur used the pulp sulfur concentrate (SC) obtained in autoclave technology oxidative leaching of pyrrhotite concentrate on MMC Norilsk; as reagent-hydrophilization used tricalcium silicate (alit - 3CaO SiO2) with a flow rate of 6.4% by weight of the FCS; and as organic surfactants used a mixture of waste oil (SNO) mol. m 247.E. and the number of rings in the molecule 1,2 in the amount of 0.005% by weight of the FCS. The pulp used SC took part in solids,%: Nickel 1,23; copper 0,19; iron 9,68; total sulfur 85,4, including elemental sulfur 80,6; calcium sulfate 4,74; in solution, g/DM3: sulphur-mono 1,03; sulfur-poly 4,10; sulfur-thio 7,22, sulfur total 13,32; calcium 5,8. The mass ratio of calcium sulfate and elemental sulfur in the UK was 1:17. The number entered is CLASS="ptx2">

In this example, the extraction of elemental sulfur in the processing in class +210 μm was 82.5% and the content of sulfur 97,2%. Sulfur concentrate contained 87.1% of elemental sulfur, sulfide is 2.1%. Sulfur recovery during flotation sulphur concentrate was 97,4%.

The table below shows examples of different components used mixtures containing svezheosazhdennoi calcium sulfate and elemental sulfur, as well as its specific consumption

According to experimental results (experiments 1-3, 6-7) additive to cereulide material mixture svezheosazhdennoi calcium sulfate and elemental sulfur allows you to select 66,1-87,4% of elemental sulfur in the class plus 210 μm, favorable for the process of sulfuric melting, and get a high quality sulfur and sulfide concentrates, regardless of the type of calcium reagent-hydrophilization: sulphur concentrates contain 80,6 and 88.5% of elemental sulfur, sulfide and 2.1% to 3.8%. While removing elemental sulphur in sulphur concentrate is to 91.6-97,6%.

The comparison of the results of the experiments 6,7 with the results of experiments 1-3 table shows that the mixture svezheosazhdennoi calcium sulfate and elemental sulfur effectively work as entered in the composition obtained from the technical sulfur). Given the specificity of the technology of production and processing serosurvey materials, the option of introducing seocalcitol mixture comprising sulfur concentrate seems to be the most rational.

1. A METHOD of PROCESSING SEROSORTING MATERIAL obtained after acid autoclave-oxidative leaching of sulfide raw materials, including water treatment pulp material calcium reagent-hydrophilization in the presence of organic surfactants at a temperature above the melting point of elemental sulfur, cooling the slurry and subsequent flotation of obtaining sulfur and sulfide concentrates, characterized in that the treatment is carried out with addition of a mixture containing svezheosazhdennoi calcium sulfate and elemental sulfur at a mass ratio of calcium sulfate and elemental sulfur 1 : (8 - 100), in quantities of 1 to 25% by weight serosorting material.

2. The method according to p. 1, characterized in that the mixture obtained using sulfur concentrate.

 

Same patents:

FIELD: chemistry.

SUBSTANCE: method for separation of the elemental sulphur and sulphide concentrate from the intermediate products of the sulphide concentrates hydrometallurgy processing includes sulphur-sulphide flotation of the intermediate original pulp in order to separate the sulphur and sulphides from intermediate oxide components with forming of the sulphur-sulphide concentrate. Then the autoclave disintegration of the sulphur-sulphide concentrate pulp is carried out in the presence of reagent - sulphide hydrophilisator and at the temperature higher than melting point of the elemental sulphur. After that the sulphur flotation is carried out in order to separate the disintegrated pulp into sulphur and sulphide concentrates. Before the sulphur-sulphide and sulphur flotations the pulp undergoes the additive agitation with the reagents, the disintegration is carried out at the temperature 140-150°C.

EFFECT: effective separation of the sulphur and sulphide concentrates.

5 cl, 3 dwg, 1 tbl

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