The method of extraction of nickel and/or cobalt from the ore or concentrate

 

(57) Abstract:

The invention can be used for hydrometallurgical extraction of Nickel and/or cobalt from ores and concentrates. The proposed method involves the oxidation of the ore or concentrate under pressure at 130oC - 250oIn the presence of oxygen and an acidic solution containing sulfuric acid or a sulfate of the metal, hydrolyzable in an acidic solution, as well as halogen ions, to obtain the solution of the recoverable metal, is provided by the cheapening of the process and increase the degree of extraction of metals. 21 C. p. F.-ly, 7 Il. , 1 table.

The technical field to which the invention relates

This invention relates to the hydrometallurgical processing of ores or concentrates of metals. In particular, the object of the invention is a method of extraction of Nickel and/or cobalt from ores in the presence of halogen ions, such as chloride. The invention also concerns the extraction of Nickel and cobalt from lateritic ores.

Art

Hydrometallurgical processing of copper sulfide ores, such as chalcopyrite (CuFeS2), is complicated by the fact that for effective leaching of copper from these ores oxidation under pressure must PR is expensive neutralization. Previously attempts have been made to ensure BaselCement sulfide concentrates in relatively mild conditions, in which the sulfides are oxidized only to elemental sulfur and will not be converted later in sulfates. These attempts included the pre-processing of the concentrate at the stage of oxidation under pressure, to facilitate subsequent leaching of sulphide concentrates, as well as leaching of the concentrate in the presence of chloride ions, such as described in U.S. patent 4,039,406. In accordance with this method, the copper contained in the concentrate is converted into a solid basic copper sulfate, copper component which is extracted by the method described in U.S. patent 4,338,168. The disadvantage of the method described in U.S. patent 4,039,406 is the fact that a significant portion (20-30%) contained in the ore or concentrate of sulfide still is oxidized to sulfate, which leads to a higher oxygen demand in the leaching under pressure and the formation of sulfuric acid. Especially this deficiency adversely affects the efficiency of the processing of the poor concentrates with high content of sulphur to copper content (S/Cu).

U.S. patent 4,971,662 restrive leaching ore acidic solution, containing chloride ions and sulphate of copper, with insufflation of oxygen. Leaching is carried out at moderate temperature (85-106oC) and pressure (from atmospheric up to 173 kPa (25 psi).

In U.S. patent 3,761,566 described method of extraction of Nickel from oxide (laterite Nickel ores. The method comprises the oxidative leaching of ore at a gauge pressure of 2.8-14.4 MPa) and a temperature of 230 to 270oIn the presence of oxygen using an acidic solution containing iron sulfate (II), or sulfuric acid, and sulphate of iron (II) is oxidized to ferric sulfate (III) and hydrolyzed in acidic solution with the formation of acid used for leaching the ore, and the solution extracted metal is formed by the oxidation under pressure from the ore.

In the present invention, a method for the hydrometallurgical extraction of Nickel and/or cobalt as separate from other metals, and in combination with copper.

The invention

The object of the invention is a method of extraction of Nickel and/or cobalt from the ore or concentrate, according to which the ore or concentrate is subjected to oxidation under pressure at a temperature of from 130 to 250oIn prisutstvie the receiving solution recoverable metal. The ion source bisulfate or sulfate is chosen from the group consisting of sulfuric acid and metal sulfate, hydrolyzable in acidic solution. In the case where the raw material is placerita ore, oxidation under pressure is carried out at a temperature of from 130 to 150oC.

The concentration of halogen ions in the filtrate, the oxidation under pressure, which is recycled to the stage of oxidation under pressure is preferably maintained within the range from about 8 g/l to 20 g/l, preferably from about 11 g/l to 14 g/l and most preferably about 12 g/L.

The description includes the use of chloride. However, it should be understood that if necessary, the chloride may be replaced by bromide.

Other objectives and advantages of the invention will become apparent from the following description of preferred options for its implementation.

List of drawings

Fig. 1 - flow chart of the method for the hydrometallurgical extraction of copper, suitable for processing copper rich ores or concentrates.

Fig. 2 - flow chart of the method for the hydrometallurgical extraction of copper, suitable for processing copper ores or concentrates medium is di, allowing, along with copper, the process to extract zinc.

Fig. 4 - flow chart of the method for the hydrometallurgical extraction of copper, allows, along with copper, the process to extract Nickel.

Fig. 5 is a process diagram of one variant of the method according to the invention, used for hydrometallurgical extraction of metals from copper-Nickel sulfide concentrate.

Fig. 6 - flow chart of another embodiment of the proposed invention the method used for the hydrometallurgical recovery of metals from Nickel-copper sulfide concentrate.

Fig. 7 is a process diagram of another version proposed in the invention of the method used for hydrometallurgical extraction of metals from Nickel laterite ore.

Information confirming the possibility of carrying out the invention

In the description, with reference to Fig. 1-4, describes the main methods of extraction of copper and zinc, disclosed in pending application PCT/CA 94/00696 filed by the applicant of the present patent application, which was published after the priority date of the present invention (WO-A-96/19593), and in the patent of the Russian Federation 2137856. The present invention Rel is with reference to Fig. 1-4, versatile enough to be applied when processing a range of copper concentrates, in which the copper content ranges from low, i.e. about 15% or less, to high, i.e. about 35% or more.

In General, the method includes a stage of oxidation under pressure stage atmospheric leaching, one or more stages of solvent extraction stage and electrochemical extraction. For processing concentrates of varying quality stage oxidation under pressure should be carried out in different processing modes, namely, mode a and mode C. mode a, which is effective for leaching copper rich ores, copper on stage oxidation under pressure not leached. In mode B, which is effective for leaching copper ores of medium and low quality copper at the stage of oxidation under pressure leached.

Below is a description of each of the two modes.

Mode AND

Technological scheme of the mode As shown in Fig. 1. The method includes a stage of oxidation 12 under pressure, held in the autoclave, the stage atmospheric leach 14, stage of primary and secondary solvent extraction 16 and 18, respectively, and converted into basic copper sulfate CuSO42Cu(OH)2. This treatment is carried out with oxygen in the presence of an acidic chloride solution. To this end, in the autoclave, introducing oxygen and hydrochloric and sulfuric acid. Process temperature in the autoclave is about 130-150oC and the pressure is about 690-1380 kPa (100-200 psi). This pressure is complete and represents the sum of the oxygen pressure and vapor pressure. The aging time in the autoclave is about 0.5-2.5 hours, the process is usually carried out in a continuous mode. However, if necessary, the process can be carried out in periodic mode.

Based on thermal equilibrium and constraints on viscosity, the solids content in the autoclave is maintained at the level of 12-25%, or 150-300 g/l

Obtained in the autoclave, the suspension is released through the one or more consecutive drain tank 22, where the pressure drops to atmospheric and the temperature is reduced to 90-100oC. the Liquid part of the suspension referred to in the description of the solution phase oxidation 12 under pressure and is indicated by the number 21.

Suspension from the drain tank 22 (drain tank) filter, as indicated by the number 24, and the resulting filtering the solid residue & rdquo; the KTA oxidation under pressure after filter 24 recycle on stage oxidation 12 under pressure, taking about 5% recycled filtrate, as shown by the number 26. The number selected on the stage 26 of the filtrate is determined proceeding from the content in the ore or concentrate soluble metals, which can dissolve at the stage of oxidation 12 under pressure. Selected filtrate 26 at the stage 28 is treated with lime to remove contained in copper concentrate metals, for example zinc and magnesium, in the form of solid residues, thereby preventing the accumulation of these metals in the cycle of oxidation under pressure. The cycle of oxidation under pressure begins from the stage 12 oxidation under pressure, followed by the stage of issue of the suspension to drain the tank 22 (tanks), filter 24, filter 26 of the filtrate, and the cycle stage 12 oxidation under pressure. The whole cycle is marked by the number 23.

Before carrying out stage 28 processing of selected filtrate 26 it is subjected to extraction 27 solvent. Using a suitable extracting agent, selected from the filtrate 26 is extracted with a solvent copper. This stage 27 of the extraction solvent technologically linked with the stages 16 and 18 of the extraction solvent and will be described below together with them.

Before the introduction of the stage 12 oxidation under pressure copper contentstudio 325 mesh, that, in turn, corresponds to the size of P80 (passing 80% of the particles through a sieve with an aperture of 15 μm). Regrinding 30 carried out in a solution recycled to the oxidation under pressure after stage 28 of the selected processing of the filtrate. The suspension obtained in stage 28 processing of selected filtrate, separated into liquid and solid phase (stage 32), the selected solution is directed to stage 30 cosmelenia, and the solid residue deposited from selected filtrate containing zinc and magnesium, is sent to waste, as shown by the arrow 17.

The solution is returned to the step 30 cosmelenia is alkaline chloride liquid having a pH approximately equal to 10. The use of this fluid helps reduce the introduction of water in the cycle 23 oxidation under pressure, which is an important factor in maintaining thermal equilibrium and conservation of chloride ions in the solution used in cycle 23.

Above it was noted that the copper on stage 12 of the oxidation under pressure not leached, and turns into an insoluble basic copper salt. The solution introduced into the autoclave at a stage 12 oxidation under pressure and which is the solution recirculated from the stage 24 of the filter 24, indicated in the diagram nomi does not occur, that is, the process proceeds so that the copper content in the input stage 12 of the oxidation under pressure of the solution 25 was equal to the concentration of copper in solution 21 oxidation product 12 under pressure. This condition is expressed by the equality [C2+] = 0.

A solution of 25 entered on stage 12 of the oxidation under pressure contains about 15 g/l copper and 12 g/l of chlorine together with approximately 30-50 g/l of sulfuric acid. Acid is introduced in the form of standard (93%) sulfuric acid. A solution of 21 oxidation product 12 under pressure also contains approximately 15 g/l copper and 11-12 g/l of chlorine, but at pH approximately equal to 3. In solution 21 virtually no acid, because it is at the stage 12 oxidation under pressure is spent on the formation of basic copper salt.

As noted above, the solution 25, the input stage 12 of the oxidation under pressure, is composed of recycled filtrate and added to sulfuric acid. The direct result of adding the acid to the filtrate is increasing the acidity of the filtrate is introduced into the autoclave for stage 12 oxidation under pressure. However, the most important consequence of the addition of an acid or sulfate ions were suddenly holding contained in cu, oxidized approximately 25-30% of the sulfur contained in the concentrate. This case relates to the method described in U.S. patent 4,039,406. However, if you add acid oxidation of sulfur to sulfate is reduced to about 5-10%. This improvement has a significant positive impact on the effectiveness of hydrometallurgical extraction. The oxidation of sulfur to sulfate causes an additional increase in costs for several reasons, for example, due to the need for oxygen as the oxidant, the necessity of introducing additional reagent to neutralize the acid formed as a result of the oxidation of sulfur, and the need of heat released during the oxidation of sulfur to sulfate, which has a pronounced exothermic in nature. This fact limits the performance of the autoclave in which carry out the oxidation of 12 under pressure.

It is believed that the addition of the acid changes the nature of the chemical conversion stage 12 oxidation under pressure as follows:

without adding acid:

3CuFeS2+21/4O2+2H2O-[CuSO42Cu(OH)2] +3/2Fe2O3+5So- (1)

with the addition of acid:

3CuFeS2+15/4O2+H2O+H the precipitate in the form of basic copper salt, which, as it contains mainly basic copper sulfate.

Apparently, in a first reaction, sulfate, basic copper sulfate formed by the oxidation of sulfur contained in the raw concentrate, whereas in the second reaction he formed sulfate ions contained in the acid, which is injected into the autoclave, which prevents the oxidation of sulfur to sulfate. Thus, in the second reaction sulfate ions completely transformed into basic copper salt. The quantity of sulfuric acid required to prevent oxidation of sulfur, established experimentally, and is about 25-75 g/l depending on the type of concentrate and the percentage of solids in the concentrate.

When conducting field experiment the actual oxidation of sulfur was higher than theoretically calculated according to the equations of both reactions. According to the first equation of the oxidation reaction to oxidize one-sixth part or 16.7% of sulfur, while the results of the experiment, the oxidation of sulfur is 25-30%. In the case of the addition of an acid, as shown by the experiments, is oxidized to sulfate is not 0% sulfur, which in theory would be right, if the second reaction, as the installed above equations do not reflect exactly the processes, what is happening in reality on stage 12 of the oxidation under pressure, and give only a rough picture.

In cycle 23 oxidation under pressure is maintained, the maximum amount of chloride, however, is usually about 3-10% chloride passes into the solid phase and is lost at the stage 24 of the filter. Thus, loss of chloride should be replaced by the introduction of hydrochloric acid or any other source of chloride ions to maintain in the input solution 25 chloride content at the level of 12 g/L. Loss of chloride is reduced by thorough washing of the solid product stage 12 oxidation under pressure stage 24 of the filter. The amount of wash water is limited by the need to maintain water balance in the cycle 23 oxidation under pressure. In cycle 23 loss of water occurs only in the form of steam 9 at the stage drain 22 and the solid residue allocated to stage 24 of the filter. Hence the need to use for dilution of the concentrate at the stage 30 cosmelenia solution recycled from stage 28 processing of selected filtrate, which minimizes the transfer of the concentrate water on stage 12 of the oxidation under pressure.

To counter the loss of chloride in the composition of the solid ostore 21 oxidation product 12 under pressure, at least at the level of 15 g/L. Loss of chloride is possible, when contained in a solution of copper not enough for the formation of basic copper sulfate, when this occurs the following reaction:

4CuCl2+6N2On-CuCl23 C satellite(OH)2+6HCl - (3)

This reaction can be counteracted by introducing into the autoclave during the oxidation of 12 under the pressure of the amount of acid in a quantity sufficient to maintain at least the minimum sufficient amount of copper in solution, providing a stoichiometric ratio of copper ions and chloride, as components of chloride of copper. When the content of chloride in the solution is equal to 12 g/l, stoichiometric copper content is determined from the relation

63,5/7112-10,7 g/l si

Thus, the content of copper in a solution of 15 g/l, is the minimum allowable to prevent significant loss of chloride in the composition of the basic copper salt of hydrochloric acid.

On the other hand, to counteract the formation of sulfur copper CuS in the reaction of elemental sulfur with an aqueous solution of copper sulfate, the copper content in the solution 21 oxidation product 12 under pressure you need to maintain as low as possible. Sulfur copper obrazovyvat is then:

3CuSO4(aq. )+4So+4H2About= 3CuS(TV. )+4H2SO4- (4)

This reaction is particularly undesirable, since sulfur copper is insoluble in the acid environment, characteristic of stage 14 atmospheric leaching. In this case, the copper is removed, goes into the final precipitate and lost.

To counteract the formation of sulfur copper CuS you want to save the content of copper in the solution 21 oxidation product under pressure at a lower level, i.e. below 30 g/l for some concentrates. The tendency to form sulphurous copper, obviously, depends on the type of processed concentrate, and the concentrate medium - high quality more prone to the formation of sulfur and copper. Thus, if the poor concentrates with a high content of copper in the solution 21 oxidation product under pressure is not a problem, for richer concentrates with a high content of copper in the solution 21 oxidation product under pressure is unacceptable.

It is now known that the processing of rich copper concentrates, i.e. containing more than 35% of copper, preferably carried out at as low as possible (i.e. below 25 g/l) the concentration of copper in solution 21 product okite 23, value of 15 g/l, the optimal range of copper content in the solution for the rich concentrates borders 15 and 25 g/l For concentrates of average quality, this interval can be substantially extended in the direction of greater border, and poor ore copper content in solution is not critical.

The content of copper in the filtrate 29 oxidation product under pressure can be adjusted by simply adding the required amount of acid in the solution 25, the input stage 12 of oxidation. With increasing amounts of added acid dissolution basic sulphate of copper leads to an increase in the copper content in the solution:

CuSO42Cu(OH)2(TV. )+2H2SO4-3CuSO4(aq. )+4H2O (5)

Adding to the acid solution in a proportion of about 1 g/l leads to an increase in the copper content in the solution of about 1 g/L. Really necessary concentration of the added acid is determined empirically on the basis of [Cu2+] = 0 and comparing the results of the analysis of the content of components in the solution 25, the input stage 12 of the oxidation under pressure, and a solution of 21 oxidation product 12 under pressure. The volume of the solution, providing cycle 23, is determined from the condition of maintaining the on stage 12 of the oxidation under pressure, can be changed at will. The solid phase weight of the concentrate fed to stage 12 oxidation under pressure, determine, based on planned volume of extraction of copper. The mass of the solution is mainly determined by thermal equilibrium process at stage 12.

The desired operating temperature at the stage 12 oxidation under pressure is 150oC and heating should be provided mainly by the heat of reaction of sulfide minerals with oxygen under high pressure in an autoclave. For the rich copper concentrates to be processed in the mode And method, this means a relatively low ratio of sulfur to copper S/Cu and, therefore, less heat of reaction per tonne of copper processed in the autoclave. The largest part of the heat of reaction released in the oxidation of no copper, and the other two main components of the concentrate, namely iron and sulfur. If the content of copper in concentrate large, then the ratio of S/Cu and Fe/Cu is low, therefore, the heat of reaction is also reduced.

Since the primary means of controlling heat transfer at the stage 12 oxidation under pressure is water, smoldering under pressure, recycled from the stage 24 of the filter, operating, regulating the amount of heated water. Cooling or heating of the suspension inside the autoclave indirect means, for example, by heating or cooling coils, it is impractical due to the rapid formation of scale on all surfaces, especially in heat exchangers, leading to significant deterioration of heat transfer. Direct heating or cooling by injection of steam or water is also unsuitable from a practical point of view of the conditions for maintaining the water balance of the cycle. Therefore, it is necessary to maintain thermal equilibrium by bringing the quantity of heat released in the reaction, in accordance with the heat capacity of the input stage 12 of material that is recycled solution 25 and the suspension concentrate. The main adjustable parameter in this case is the flow rate of the feed solution 25. This is one of the features that distinguish the mode And mode C. In the following mode, where the extent of oxidation of sulfur greater warmth in terms of per tonne of copper product is secreted in greater quantity. This allows you to enter the stage 12 oxidation under pressure greater amount of solution 25.

Was established the feasibility of introducing into the autoclave at a stage 12 oxidation under the pressure of small amounts of certain surface-active substances, which alter the physical and chemical properties liquid elemental sulfur (So). Such surface-active substances, such as lignin sulfonate, quebracho added in small quantities, i.e., 1-3 g/l, in the input stage of oxidation under the pressure of the solution 25 can reduce the viscosity of liquid sulfur, as well as to change the chemical processes in the autoclave.

The addition of surfactants can reduce the oxidation of sulfur. This effect has a positive effect on the efficiency of the process, although its nature is not quite understandable. This might be explained by the decrease of the viscosity, which liquid sulfur and particulates are less likely to linger in the autoclave. As a consequence, decreases the residence time of the material in the autoclave and, accordingly, the tendency of sulfur to oxidize.

Also found that with the introduction of surfactants copper minerals react more fully, which is why sigevalee desirable reaction pass through.

Equation (5) describes the reaction, which is based on the regulation of the content of copper in the filtrate 29 by adding sulfuric acid in a solution of 25 entered on the stage of oxidation under pressure. The overall oxidation reaction occurring during the oxidation of chalcopyrite ore under pressure with the introduction of sulfuric acid, expressed by the above equation (2)

When used as a source of sulfate ions instead of sulphuric acid, sulphate of copper is similar to the reaction:

3CuFeS2+15/4O2+3H2O+3/2CuSO4-3/2CuSO42Cu(OH)2+3/2F2O3+6So(6)

It should be noted that in reaction (6) requires 3/2 mole of sulphate of copper sulfate compared with one mol of sulfuric acid in the reaction (2). Therefore, if instead of sulfuric acid as a source of sulfate ions is provided to use copper sulfate, its molar quantity should be one and a half times more than in the case of sulfuric acid. To account for this, the inventor has developed the concept of equivalent excess sulfate, allowing the calculation taking into account equation (6) the amount of acid that must be added to the solution 25 entered on the stage of oxidation under pressure, for Costigan is required to keep the copper content in the filtrate 29 oxidation product under pressure. Below is disclosed useful result using the concept of equivalent excess sulfate.

Equivalent excess sulfate is the amount of free sulfate in the input stage of oxidation under the pressure of the solution 25, free for the formation of basic copper sulfate on stage 12 of the oxidation under pressure. Free is the sulfate, which is in excess relative to a certain base level of copper sulfate CuSO4and copper chloride CuCl2.

Basic level CuSO4and CuCl2is the number of sulfate sufficient to maintain the content of chloride 12 g/l in solution in the form of copper chloride and, in addition, maintain the copper content, is approximately equal to 4.3 g/l solution in the form of copper sulfate. The concentration of copper chloride CuCl2corresponding to 12 g of chloride per 1 liter of solution, is 134,5/7112= 22,7 g/l, of which 10.7 g/l accounts for copper. Thus, the addition of this number with an additional 4.3 g/l gives a value of 15 g/l total copper content in the General solution of sulphate and chloride of copper, characterizing the underlying level.

Then the amount of free sulfate is defined as the total amount of sulfate in the form of copper sulfate, meanie free sulfate is defined as: 28-15= 13 g/l of copper. Multiply this number by 98/63,5 20 g/l (concentration2SO4as free of sulfate of the composition of copper sulfate.

Then by dividing the free sulphate of copper sulfate 1.5 calculate the equivalent amount of excess sulfate.

Equivalent excess sulfate = { free sulfate in the form of copper sulfate} /1,5

Thus, in this example, when the total copper content of 28 g/l or the amount of free sulfate of the composition of copper sulfate 20 g/l equivalent excess sulfate of the composition of copper sulfate equal to 20/1,5= 13.3 g/l

So, if the equivalent of the end of the free acid in the solution 25 entered on the stage of oxidation under pressure is, for example, 52 g/l of sulfuric acid, the required concentration of the acid is defined as 52-13,3= of 38.7 g/l H2SO4where to 13.3 g/l equivalent of excess sulfate. The obtained value of 38.7 g/l) is the amount of acid that must be added to a solution of 25 entered on the stage of oxidation under pressure, to maintain the copper content in the filtrate 29 oxidation product under pressure, i.e. the base level of 15 g/L.

When used as a source of sulfate ions instead of sulfuric acid sulfuric acid recyclage zinc assumed since zinc is hydrolytically converted to basic zinc sulfate, ZnSO43Zn(OH)2that is the basic zinc salt, by analogy with the basic copper sulphate. Below these reactions described by equations (7) and (8).

3CuFeS2+15/4O2+2H2O+1/3Fe2(SO4)3- CuSO42Cu(OH)2+11/6F2ABOUT3+6So(7)

3CuFeS2+15/4O2+13/3H2O+4/3ZnSO4- CuSO4Cu(OH)2+6So+Fe2O3+ 1/3{ ZnSO43Zn(OH)24H2O} (8)

The solid oxidation product 12 under pressure after the filter 24 is subjected to atmospheric leaching of 14 at pH of about 1.5 to 2.0. Leaching 14 use acidic raffinate from the first stage 16 solvent extraction, solvent basic copper sulfate. Leaching 14 is carried out at a temperature of approximately 40oWith for about 15-60 minutes. The solids content is approximately 5-15% or is 50-170 g/l, although the process can be performed for values outside this range.

During atmospheric leaching of 14 basic copper salt dissolved almost completely, from the available concentrate of iron in the solution passes his very small amount.

It is established that the extraction of copper from raw concentrate, coming on stage 12 of the oxidation under pressure, is approximately 95-98%. It was also established that the transition of iron in the solution is approximately less than 1%.

Suspension 31 obtained at the stage atmospheric leach 14, it is difficult, if not impossible, to filter, but it is well defended. Due to the need for very thorough rinsing passed through the leaching of the solid phase of the suspension 31 is injected into the cycle of countercurrent washing by decantation, denoted for simplicity in Fig. 1 as the separation stage 34 solid and liquid phases. In the cycle of counter-current decantation 34 solid phase is passed through a series of thickeners with wash water, moving in the opposite nag the captured content of the solution in the final balance relative to copper to less than 100 ppm, you must have approximately 3-5 thickeners (not shown) when the ratio of wash water to the solid phase, is approximately equal to 5-7.

The condensed product from the last thickener is the final residue 35, containing about 50% solids. It can be processed to extract precious metals such as gold and silver, or sent to waste. For recovery of noble metals can be used known methods, for example, cyaniding. The main components of stream 35 are hematite and elemental sulfur, which can be removed by flotation, if market conditions allow.

The top product from the first thickener is a solution of 33 directed, as shown in the diagram, the first stage 16 of the extraction solvent. In one variant of this solution contains approximately 12 g/l of copper, 1 g/l chloride and 0.5 g/l of iron.

The optimum copper content is determined by the ability to extract from a solution of 33 maximum amount of copper on stage 16 of the extraction solvent. Because one of the fractions of approximately one third of the raffinate from the solvent extraction 16 solvent, eventually neutralized, it is important Bhagat diluted copper solutions because with a large copper content in the raffinate solution after extraction solvent has a high acidity, which in turn leads to a decrease in the efficiency of extraction. However, the treatment is more concentrated copper solutions cheaper, from the point of view of capital costs, as more concentrated solutions take up less volume. However, above a certain level increased concentration does not reduce the size of the extraction unit, because there is an upper limit of saturation of the organic extractant, and the amount of water typically support equal to the volume of organic extractant to allow mixing by recirculation of water. Therefore, the total volume of the organic extractant and the aqueous solution is determined only by the volume of the organic extractant. The uptake of organic extractant, and hence its volume, is related to its concentration and properties. Traditional solvent - diluted condition with 40% concentration by volume, for example, reagent type LIXTMproduction Corporation Henkel Corporation one pass takes about 12 g/l of copper. Thus, the concentration of copper in solution 33 shall also makes the cantali, two-stage solvent extraction. On stage 16 of the primary solvent extraction get the raffinate 37, containing about 20 g/l free acid and about 0.3 -1 g/l of copper. A large part of the raffinate 37 recycle the atmospheric leach 14, but about 25-30% of the raffinate you cannot return to the stage 14 atmospheric leaching, as this would exceed the limit of acidity. This part of the raffinate is subject to neutralization. Excess 121 is withdrawn from the recirculation line (stage 36) and neutralize.

The neutralization is carried out in two stages in order to fully extract the copper, and troubleshoot possible problems associated with environmental pollution remains of neutralization containing copper. The possibility of such contamination exists, if not extracted from the raffinate 37 copper neutralising will settle, and later re-dissolved, for example, in a pond tailings storage facility.

The first stage 38 of the neutralization is carried out at pH 2-3 using limestone, which in the role of the reagent is very cheap compared to lime. Product neutralizing filter (stage 40), and the resulting solid phase is washed with water from an external source 45. Solid phase consisting mainly of gypsum and Gertie solvent for extraction of the remaining copper. Secondary extraction 18 solvent is advantageously carried out after the first neutralization 38, and a secondary raffinate 43 contains very little copper, as a rule, approximately in the range of 0.03-0.06 g/l C.

As shown by the dashed lines in Fig. 1, at stage 18 of the secondary solvent extraction employing the same organic extractant that on stage 16 of the primary solvent extraction. In addition, the extractant is also involved at the stage 27 of the extraction solvent selected from the filtrate 26 oxidation product under pressure. The organic extractant, which is washed on the stage 42 wash water 122 from an external source 45 and is cleaned at step 44, is returned to the step 18 of the secondary solvent extraction, and then comes on stage 16 of the primary solvent extraction. Purified organic extractant 125 share, directing one part of the stage extraction 27 solvent. Before washing 42 raffinate from the extraction 27 solvent added to a saturated copper on stage 16 solvent extraction organic extractant 123. Wash water 47 after washing 42 is directed to the stage 24 of the separation of the oxidation product under pressure into solid and liquid phases using it on this is ilenia under pressure, that allows you to extract copper and chloride from the flushing water 47, used in the extraction step with a solvent.

The raffinate 43 from the secondary extraction 18 solvent re-neutralize stage 46 of the secondary neutralization, and this time, the pH is equal to 10, and filtered (stage 48), removing dissolved heavy metals. A solution of 51 allocated at stage 48, is used as wash water in the loop 34 countercurrent decantation to launder closing balance 35 from leaching. As shown by the arrow 53, the solid residue allocated to stage 48 of the filter is sent to the dump.

Cleaning 44 from copper-rich and copper-washed organic extractant conduct consumed at stage 20 electrochemical extraction of the acid or electrolyte, resulting in obtaining not containing impurities a solution of copper sulfate or saturated electrolyte 57, which is then sent to stage 20 electrochemical extraction carried out in the usual way.

The diagram shows that all the solutions are reused, cycles of all solutions is closed. The blade is sent only solid residues.

Mode

In Fig. 2 presents tekhnologicheskaia denoted by the same reference numbers. For example, the oxidation step under pressure here again indicated by the number 12, the stage atmospheric leach - number 14, stage electrochemical extraction - number 20, the drain tank (tanks) - number 22, filtering oxidation product under pressure - the number 24, the processing of selected filtrate 29 oxidation product under pressure - number 28, stage grinding - room 30, and the cycle of countercurrent washing by decantation number 34.

In this mode of implementing the method oxidation 12 under pressure is conducted for the purpose of oxidation greater part of the copper contained in the raw concentrate, and with a view to its leaching into the solution. Usually the solution is transferred approximately 85-90% of copper, and only 10-15% of copper goes into the remainder in the form of a basic sulfate of copper.

The conditions created in the autoclave at stage 12 oxidation under pressure regime, similar to that created in the mode a, except smaller solids in the treated suspension - 150-225 g/L.

In this mode, the index [si2+] usually equal to 30-40 g/l, i.e., in solution 21 oxidation product 12 under the pressure of the copper content of more than introduced into the autoclave the solution. One liter of the solution 25, the input stage 12 okelani mode, displayed in Fig. 1, in this mode sulfuric acid from an external source on stage 12 of the oxidation under pressure is not administered. In this mode, the acid recycle, i.e. use the filtrate 29 oxidation product under pressure again. One liter of the solution 21 oxidation product 12 under pressure contains about 40-50 grams of copper and 11-12 g chloride at pH approximately equal to 2-2,5.

The concentration of copper in solution 21 from the leaching stage 12 oxidation under pressure must be regulated to provide the desired distribution of copper between the solution (85-90%) and the remainder (10-15%). With this distribution in the residue from the leaching there is a small but important amount of solid core of copper sulfate. Because copper sulfate is a salt buffer, its presence is convenient to estimate the pH. In the case of a concentrated solution of copper sulfate finding pH in the range of 2-2,5 indicates the presence of a basic sulfate of copper. If the pH is below 2, almost all of the basic copper sulfate dissolves, and when the pH is higher than 2.5 is too much sulphate of copper, resulting in the likely depletion of the solution 21 copper.

The main factor regulating the content of the copper awlad, regulate the degree of neutralization of the raffinate remaining from the extraction solvent of the filtrate 29 oxidation product under pressure, which is discussed below. Typically, depending on the required amount of acid must be neutralized by about 25-50%.

The formation of acid at the stage 12 oxidation under pressure processing of various concentrates and under different process conditions vary from place to place. If stage 12 oxidation under pressure from concentrate a large amount of acid to achieve the desired result, the solution 25, the input stage 12, may contain less acid. The minimum amount of copper (contained in the raw concentrate), which should go into solution 21 is 10%. Following these 10% pH drops so that the filtrate 29 oxidation product under pressure dramatically increases the iron content. Typically, the iron content is approximately 10-50 ppm, but if the pH dropped below 2 and the remainder loses basic copper sulfate, iron content quickly grows to over 1 g/L. This is undesirable, because there are several elements forming an impurity, such as arsenic and tiboni, Kotor is a sure sign of a low content of impurities in the filtrate 29 oxidation product under pressure. In addition, the iron itself is an impurity, and its presence in cycle 20 electrochemical extraction is very undesirable.

There is another factor limiting the maximum concentration of copper in solution. Unexpectedly, it was found that at low concentrations of copper in the solution of some really concentrates more willing to give copper. The reason for this is seen or the formation of secondary sulfur copper CuS, as mentioned above, or some other phenomena associated with low rates of oxidation of the primary mineral, chalcopyrite, in solutions with a high content of copper. It is established that formed during the reaction stage 12 oxidation under pressure elemental sulfur can cover or actually encapsulate unreacted particles of chalcopyrite and impede their contact with the reagents. The consequence of this is the low copper recovery. Apparently, this effect is reinforced by the high energy levels of copper ions in solution. To eliminate or mitigate possible by the use of surfactants, as described above. For some concentrates, in particular, the rich, this problem is more acute than others. Therefore, these eat (so that is more than 95%). This requires that a significant portion of the copper was present as a basic sulphate of copper, i.e., was not in the filtrate of the oxidation product 12 under pressure, and a solid residue. Usually in a solid product, if necessary, can be translated 20-40% copper, thereby ensuring that the content of copper in solution at a level low enough to achieve high recovery of copper.

The problem of low copper recovery in case of high content of copper in the solution relevant to more rich concentrates. Therefore, while improving the quality of concentrate an increasing proportion of copper to be transferred to the solid product. This dependence explain the experimental results (see table) with three different concentrates.

In a molar ratio of N+/C indicator N+applies to input into the process acid, and the si raw material concentrate. All ions H+in the input acid are considered as protons, which became free when the full dissociation of the acid, even if the existing conditions acid dissociable incomplete. The values of H+/Cu shown in the table reflect the experimentally determined optimum level, ensuring Costigan is stratov, mode has been selected And the way in which all the copper goes into solution 33, a [Cu2+] = 0. The molar ratio of N+/C has the value set experimentally as ensuring the achievement of the desired result: [si2+] = 0.

For processing the second concentrate belonging to the class concentrates medium quality mode has been selected In the way, but a significant portion of the copper turned in a solid basic copper sulfate. This was achieved by maintaining a relationship of H+/C at a level low enough to prevent the dissolution of all the copper in solution.

For processing of the third concentrate belonging to the class of poor concentrates, was also selected mode In the method, but in this case, due to rather high values+/C in the remainder passed the minimum amount of copper.

The solid residue of the oxidation product 12 under pressure is subjected to leaching 14, recycled from stage 16 solvent extraction the raffinate 37, which is a dilute acid with a content of 3-10 g/l of sulfuric acid. Since most of the copper after stage 12 oxidation under pressure passes into the filtrate 29, and only a small her time is 14 I quite insignificant. Accordingly, and in the raffinate 37 from the extraction of 16 solvent content of copper is also insignificant. Typically, one liter of the solution 31 after atmospheric leaching contains 3-7 g of copper and 0.2-0.5 g of iron.

As in mode A, the suspension coming from the stage 14 atmospheric leaching, difficult to filter. However, using a number of thickeners, forming the installation of 34 countercurrent decantation, it is possible to achieve good separation of solid and liquid phases and washing the solid phase. Flush water 51 flows from the stage 16 extraction

the solvent in the raffinate, which is subjected to neutralization at stage 46. This process is similar to the process conducted according to mode A. the Only significant difference is the lower grade ore in a solution of 33 and a smaller volume of solution.

A solution of 33 generated on stage 14 atmospheric leaching, is subjected to extraction 16 solvent. Copper-containing solution 29 obtained in stage 12 of the oxidation under pressure, is subjected to solvent extraction stage 50. Thus, In the method involves two stages 16 and 50 solvent extraction, through which two different flow Rast, is that at both stages 16 and 50 share of organic extractant.

As shown in Fig. 2, the organic extractant 125, peeled from the copper phase General cleaning 44, first recycle in cycle 16 solvent extraction for the extraction of copper from the weakest copper-containing aqueous solution 33, so as to effectively extract copper from such solution extractant should be as free from copper.

Then copper-containing organic extractant 126 from the stage 16 solvent extraction direct to the stage 50 solvent extraction, where it is in contact with a solution of 29 containing copper in larger quantities. At the stage of 50 solvent extraction is not required to achieve a high degree of extraction, since the raffinate 63, as shown in the diagram, recycle on stage 12 of the oxidation under pressure. Unlike the raffinate 63 raffinate 37 recycle after extraction 16 solvent only partially, as part of its neutralized at the stage 46 in order to remove from the cycle of excess acid. Therefore, it is more important to achieve a high degree of extraction of copper on stage 16 solvent extraction.

As in mode A, the raffinate 37 after extraction 16 solvent p is atmospheric leaching. An important difference between this mode And is that the copper content in the raffinate 37 from the extraction of 16 solvent sufficiently small, i.e. less than 100 ppm, so there is no need before neutralization 46 to conduct secondary stage solvent extraction, as in mode A. One-stage solvent extraction is sufficient due to the low content of copper in the solution and a small volume of the solution, which allows for the extraction of 16 solvent with greater completeness of extraction,

Copper-containing organic extractant 65, sequentially passed through two stages 16 and 50 of the extraction solvent, is subjected to two-stage countercurrent washing (denoted in the diagram by block 42) aqueous solution 122 diluted acid. The main purpose of this washing is to remove captured copper-containing organic extractant 65 aqueous solution and, in particular, the reduction of the chloride content at the stage of purification 44 organic extractant from copper. Required amount of wash water is approximately 1-3% of the volume of the organic extractant. A solution of 47, obtained after washing, recycle on stage 12 of the oxidation under pressure.

At stage 44 washed the organic EXT aluca not containing impurities of the copper solution or saturated electrolyte 57, from which copper is extracted conventional electrochemical method.

To achieve a desired molar ratio of H+/C raffinate 63 at the stage 70 is divided into two parts 72 and 74. Part 72 of the raffinate recycle on stage 12 of the oxidation under pressure. Part 74 of the raffinate is subjected to neutralization 76 limestone at pH 2. The solid residue is washed and sent to the dump, as shown by the arrow 80. The filtrate 82 product neutralization connect with a part 72 of the filtrate and recycle as solution 25 to the stage 12 oxidation under pressure.

Thus, the present invention first proposed to use total organic extractant for the extraction of copper from two different aqueous solutions. This allows significantly reduce the process of solvent extraction by reducing capital and operational costs. In addition, it allows you to use in the loop countercurrent washing by decantation of the product of the atmospheric leaching large amounts of water, which makes possible to wash out the final balance and to extract from such a diluted copper-containing solution, an additional amount of copper.

The degree of oxidation of sulfur to study the quality or mineral composition, and conditions of the oxidation steps 12 under pressure. For specific concentrates are characterized by a very high degree of oxidation of sulfur, i.e., oxidation contained in concentrate sulfur to sulfate, and it was observed that such concentrates are characterized by low (less than 28% by weight) copper. The inventor found that the oxidation of sulfur depends not so much on the content of copper in concentrate, but on the relationship of copper to sulfur content. Due to the fact that copper ore usually consist of chalcopyrite with other minerals, particularly pyrite FeS2or pyrrolidon FeS, the main impurities of copper concentrate are iron and sulphur.

Mode In the problem of excessive oxidation of sulfur on the oxidation steps 12 under pressure at the poor handling of concentrates is solved by the deliberate dissolution of 90% copper and reduce the formation of basic copper sulfate. In the case of treatment of chalcopyrite reaction is:

CuFeS2+5/4O2+H2SO4= CuSO4+1/2F2O3+2So+H2(9)

Thus, the filtrate 29 oxidation product 12 under pressure contains a lot of copper sulfate and copper chloride, and it is treated with the Dios electrochemical extraction 20.

In Fig. 3 is a flow diagram of a method for the hydrometallurgical extraction of zinc along with copper. The stage of this variant of the method, corresponding to the stages of the previous variants, denoted by the same reference numbers.

As in the previous embodiments, the concentrate is subjected to regrinding 30.

Oxidation of mixed copper-zinc concentrate under pressure is conducted similarly to the oxidation of the concentrate, containing only copper, technological scheme of which is shown in Fig. 2.

The zinc is oxidized as easily as copper, or even faster, and more goes into solution 29 from leaching than in the solid residue from the oxidation under pressure. This is because the zinc in the form of the basic sulphate of zinc is less than copper, is prone to hydrolysis, i.e., the hydrolysis proceeds at high pH values.

The high content of ore components in the solution is not explicitly complicates the extraction of copper and zinc, as established in the case of solutions with a high content of copper. Therefore, the transition mostly copper and zinc in the filtrate 29 oxidation product under pressure, i.e., as the regime is acceptable. The oxidation number of sulfur is low, p is to obtain a high ratio of H+/C, it is necessary to recycle almost all the acid remaining after the extraction step 16 solvent, with its minimal neutralization. The content of sulfuric acid in the input solution can reach 75 g/l when the copper content equal to about 10 g/l, the zinc content is about 5 g/l and the chloride content of about 12 g/L.

The filtrate 29 oxidation product under pressure contains significant amounts of both zinc and copper, depending on the composition of the raw concentrate. When the concentrate contains 20% copper and 5% zinc, the filtrate 29 oxidation product under pressure may include approximately 50 g/l of copper, 15 g/l of zinc and 12 g/l of chloride.

The remainder of the oxidation product under pressure leached at stage 14 in a similar manner, using the raffinate from 37 extraction 16 solvent and receiving mixed copper-zinc solution, administered in cycles of solvent extraction. First remove the zinc, and then copper.

As used in the processing of copper concentrates through the stages of solvent extraction are two water flow. The filtrate 29 oxidation product under pressure contains a lot of copper and zinc, while in a solution of 33 product of atmospheric leaching of such scheme, used in the above-described embodiments of the method, the added phase extraction of zinc solvent, i.e. an organic extractant is introduced into contact first with a weak solution, and then with a strong aqueous solution. In this case, the technological scheme of solvent extraction is divided into two cycles: one for the extraction of zinc and the other for the extraction of copper.

Copper can be extracted first, and after it is zinc, which depends on the choice of the organic extractant and its affinity with respect to these two elements. The applicant had the possibility of obtaining satisfactory results when used as the first extractant diethylhexylphthalate acid, which selectively takes zinc in the presence of copper. For this reason carried out two stages of extraction 100 and 102 diethylhexylphthalate acid, the first stage 100 extraction of zinc solvent was subjected to a weak solution of 33, and the second stage 102 is a stronger solution 29 obtained at the stage of oxidation 12 under pressure, and the principal amount of copper remained in solution.

Extraction of zinc using diethylhexylphthalate acid is complicated by the low efficiency of extraction under conditions of highly the tion of sulfuric acid, about 7-10 g/L. To solve this problem in a cycle of extraction of zinc solvent included intermediate stage neutralization 104 at pH 2. Thus, the extraction of zinc solvent is carried out in two stages, i.e. at the stage 102 and second stage 103 with neutralizing 104 between them. At each stage 102, 103 in the extractant goes 5-7 g/l of zinc, after which the extraction solvent is stopped by increasing the pH of the raffinate. Through the use of intermediate neutralization 104 total extraction of zinc can be increased to 10 g/l or more. The raffinate 97 from the first stage extraction 102 solvent is neutralized at the stage 104 to a pH approximately equal to 2-2,5, inexpensive limestone (caso3) to obtain solid particles of gypsum, which sucked stage 98 and removed. Then the filtrate 99 served on the second stage extraction 103 solvent. Typically, the filtrate entering the second stage solvent extraction, contains 10 g/l of zinc and 50 g/l of copper at pH approximately equal to 2-2 .5. After extraction of the second raffinate 124 contains, typically, 5 g/l of zinc, 50 g/l copper and 8 g/l acid.

For cycle extraction 16 solvent content of zinc in the solution is small enough, so Etnies is mainly determined by the efficiency of the cycle extraction of zinc solvent. Due to the fact that zinc is bad enough removed have extractants (e.g., diethylhexylphthalate acid), there is some limit on the amount of zinc, approximately 5-7 g/l, which can be extracted before the reaction stops due to the accumulation of acid in the raffinate. For further extraction of zinc required neutralization of this acid. The use of intermediate neutralization allows you to extract much more of zinc, however, the intermediate neutralization removes from the cycle sulfate, the loss of which must be replenished either by the oxidation of sulphur, or the introduction of cycle 23 oxidation under pressure fresh acid.

One intermediate stage of neutralization, probably compatible with sulfate balance, therefore, it is preferable to maintain the rate of [Zn2+] , equal to the difference between the content of zinc in the filtrate 29 oxidation product under pressure and zinc content in the recycled raffinate 72, at about 10 g/L. Thus, if the acid is introduced at the stage of oxidation under pressure in the form returned from the stage solvent extraction of raffinate 72, contains 5 g/l of zinc, the filtrate 29 oxidation product under pressure should the tion of the zinc solvent in comparison with the extraction of copper. The higher efficiency of extraction of copper by solvent means that the effective extraction of copper can be achieved at a higher content in the raffinate acid - up to 75 g/l of sulfuric acid compared to the limit of the acid content of about 7-10 g/l, specific for the extraction of zinc by solvent. Therefore, copper can be extracted from solution with a copper content of 50 g/l

After carrying out solvent extraction zinc-containing organic extractant 106 (diethylhexylphthalate acid) contains a certain amount of copper, which is explained by the relative selectivity diethylhexylphthalate acid to zinc and simply capture a strong copper solution. Typically, the ratio of zinc to copper (Zn/Cu) zinc-containing organic extractant 106 is from about 150: 1 to 300: 1. If copper is not removed, then all of it is at the stage of purification 114 solvent will leave from the organic extractant together with zinc and, thus, will get rich in zinc electrolyte 120, directed on stage electrochemical extraction 118 zinc. For the electrochemical extraction of zinc with the formation of the zinc cathode satisfactory purity at reasonable electr who should be approximately 100000: 1. For this reason, before the electrochemical extraction it is important to remove almost all of the copper or of zinc-containing organic extractant 106 or later, from the saturated electrolyte. Removal of copper from zinc-containing organic extractant 106 is much more simple operation.

Removal of copper need a few (for example, from 3 to 10, usually 5 stages of washing or processing. For washing use a dilute acidic aqueous solution of sulphate of zinc. Stage of leaching arranged in series, that is treated with an organic extractant leaving the first stage of leaching, is entering the second stage washing and so on, until the organic extractant will not come out of the last stage. Together with copper washed away a certain amount of zinc, it is therefore necessary to minimize the number of used wash water and to compensate for the lack of water to use several stages of counter-current washing.

The resulting wash solution 110 recycle in the cycle of atmospheric leaching, where the extract copper and zinc.

After washing stream 112 organic extractant (diethylhexylphthalate acid) ready for cleaning 114 from the and get rich in zinc electrolyte 120, suitable for electrochemical extraction of zinc with high electrical efficiency.

After cleaning 114 from zinc and before the recycling of the extractant on stage extraction 100 organic solvent extractant purified 131 from iron. Cleaning 131 from iron implement solution 133 hydrochloric acid, which is injected into the oxidation under pressure.

Each of the refined 122, 124, resulting from the extraction of zinc diethylhexylphthalate acid, direct on-stage solvent extraction 16 and 50, respectively, where they selectively extracted copper using a copper extractant, as LIXTM.

Technological scheme of these two cycles, 16, 50 similar cycles, carried out in mode, when the total organic extractant used first in the extraction step 16 solvent, and then in the extraction step 50 the solvent. Then, as in the previous embodiments, the copper-containing organic extractant is washed and cleaned of copper, as shown in the diagram blocks 42 and 44, respectively.

It is established that in the cycle of extraction 50 solvent no significant needs in the neutralization, since the neutralization is carried out before the extraction ZiT as well as in the previous embodiments of the method, the stage of oxidation of 12 under pressure and stage atmospheric leach 14, respectively.

In Fig. 4 is a flow diagram of the next version of the proposed method for the hydrometallurgical extraction of copper associated with the extraction of Nickel. The stage of this variant of the method, corresponding to the stages of the previous variants, denoted by the same reference numbers.

The method of processing copper-Nickel concentrates is very similar to the method of processing of zinc concentrates, except that all available extractants in relation to Nickel have less selective extracting action than with respect to copper. Therefore, both cycle extraction 130, 132 Nickel solvent is carried out after the respective cycles of extraction 16, 50 copper solvent.

Nickel extractant 135 obtained in the extraction step 132 solvent, washed (stage 137), and then before recycling to the extraction 130 solvent was purified from Nickel (stage 139). Cleaning 139 from Nickel conduct spent on stage electrochemical extraction 140 Nickel electrolyte.

In addition, the extraction of Nickel enough neznachitelinoe 134 and 136, respectively. Ammonia must be regenerated from the corresponding refined, for example, by the lime boil 138, and recycling.

It is established that there is a limit to the degree of oxidation of sulfur attainable in mode C. When the oxidation number of sulfur is quite high, and during the oxidation under pressure, a sufficiently acid, after the stage of oxidation under pressure there is some excess acid, for example, in the form of sour raffinate, even when the acid is not introduced from the outside. In this case, not only all contained in concentrate copper go into the dissolved copper sulfate, but also a certain amount of iron is also dissolved by the excess of acid with the formation of, for example, sulphate of iron.

It is desirable that contained in concentrate iron is not passed into a solution of the oxidation product under pressure, where it had to be removed selectively from copper, and the solid residue product of the oxidation under pressure in the form of stable hematite Fe2O3. In the traditional concentrates the content of copper and iron Fe/Cu is at least one-to-one, hence the importance of economical and fully removed from the iron, using the mechanisms of co-adsorption or coprecipitation.

However, it was found that during the processing of some concentrates oxidation of sulfur (education acids) is so intense that exceeds the requirement phase oxidation under pressure in the acid, and a certain amount of iron goes into solution even in the face of the regime Century the Task of this method is the provision of low iron content (usually 0.05 g/l) in solution. When testing some of the concentrates were obtained value content of iron of 1.0 to 12.0 g/L. Similarly, the objective of the method is to achieve a solution pH of the oxidation product under a pressure of 2.0 to 3.5, which corresponds to the content of free acid is less than 1 g/l, and when testing concentrates were obtained pH values of the solution of the oxidation product under pressure, in the range of 1.2 to 2.0, which corresponds to the content of free acid of 1-15 g/l

Thus, to process concentrates the above class is designed with another mode of the method, namely the mode C. This mode is discussed below.

Mode

Concentrates for processing have developed mode, with a pronounced tendency to oxidize sulfur processing -- which means the ratio of the sulfur content of the metal S/M, where M is the usual metals, such as copper, zinc, Nickel, cobalt, lead and others, but with the exception of iron, which is not involved in the removal of acid.

Among the concentrates processed in mode, often can include Nickel and copper-Nickel concentrates, as they are often poor, often have a ratio S/M is about 2: 1 or above. Such concentrates are also some copper or copper-gold concentrates, if they are poor because of the high content of pyrite. Also found that some copper-zinc concentrates contain a lot of pyrite and, therefore, also apply to the concentrates processed in mode C.

There is a General correlation between the content of pyrite (FeS2and the tendency of concentrates to the manifestation of symptoms, causing the need for processing in mode C. However, due to the fact that not all pyrite react the same, there are exceptions that do not fit in this ratio. Some pyrite oxidizes sulfur more actively than others. At the same time, it is known that minerals such as pyrrhotite (Fe7S8or part of the iron-zinc concentrates sphalerite (Zn, Fe)S, cause much less oxidation of sulfur and therefore suitable on the most important differences.

First, the raffinate 63 (Fig. 2) neutralize before returning to the stage oxidation 12 under pressure as a whole, i.e. not divided into one part that is subjected to neutralization, and another part, recycled without carrying out neutralization.

Secondly, the suspension of the product of the oxidation under pressure before separating the residue from the leaching subjected to additional neutralization or reversal after oxidation under pressure in order to neutralize the excess acid and precipitation of iron present in this moment, in solution in any form. Neutralization after oxidation under pressure is carried out at the maximum temperature, immediately after the release of the slurry from the autoclave. The most convenient option for such neutralization is the neutralization of the suspension in the waste-holding tank after grazing pressure to atmosphere when the temperature of the suspension is equal to the boiling point of the solution, i.e. about 100oWith, or close to it.

With this purpose, to neutralize any excess acid in the suspension of the product of the oxidation under pressure applied limestone, thus raising the pH to about 3. Simultaneously with this, there is a precipitation of all trivalent iron ions Fe3+

The resulting neutralization, the suspension is filtered, and the solid precipitate, as always, thoroughly washed with the purpose of complete removal of the captured solution (containing copper ions, chloride). The filtered solid residue is subjected to atmospheric leaching, where in traditional conditions at pH approximately equal to 1.5 to 1.8, involves leaching of deposited copper, and the balance from leaching are subjected to a thorough countercurrent washing by decantation. The filtrate 29 of Priya 50 solvent, getting the raffinate 63, which is then channelled to neutralize 76, as in the above-described embodiments, and is recycled to the stage of oxidation 12 under pressure, but without division 70 of the raffinate, as noted above. Thus, the cycle of oxidation under pressure.

The main stages of the proposed invention method can be represented as follows:

complete oxidation of all non-ferrous metals such as copper, Nickel, zinc and cobalt contained in sulfide concentrates, and iron,

- to minimize oxidation of sulfur to sulfate and the maximum increase in the formation of elemental sulfur,

- deposition of metals, corroded during the oxidation under pressure, in the form of basic salts, for example, basic copper sulfate,

- dissolution of metals corroded during the oxidation under pressure, in the form of sulfates, for example, zinc sulfate or Nickel sulfate.

Despite the fact that the oxidation under pressure flows under catalytic action of chloride, the chloride content in the solution is small, for example, requires only 12 g/l of chloride, the balance in the corresponding salts of hydrochloric acid, copper or zinc contained in overzelous sulfate ions. Thus, from the oxidation under pressure solutions are usually not purely chloride, and contain a mixture of salts of sulfuric and hydrochloric acids.

Proposed in the invention method can be used for processing concentrates containing only Nickel or Nickel in combination with copper or cobalt. Similarly, you can process copper-zinc concentrates. This is accomplished by using a rational amount of sulfate or sulfuric acid at the stage of oxidation under pressure in the presence of a halogen, such as chloride. Lack of acid or sulfate leads to undesirable increase of the degree of oxidation of sulfur, as well as to reduce the oxidation state of the metal and, therefore, the completeness of extraction of the concentrate. The consequence of excess acid is the dissolution of iron contained in the suspension of the oxidation product under pressure, and increased costs associated with excess acid and neutralizer.

Copper-Nickel concentrates

Technological scheme of the method shown in Fig. 5. The method in this embodiment is designed to handle concentrates containing 3-25% copper and 3 to 10% Nickel, with a predominance of copper. Usually in concentrate is cobalt, and otiu cobalt in concentrate.

This variant of the method is, essentially, one of the types described above regime, where most of the copper is transferred during the oxidation under pressure in a solid and in solution. In order to Nickel and copper went into solution, mainly in dissolved sulfate, at a stage of oxidation under pressure, you must enter the acid. Acid is added in the input stage of oxidation under the pressure of the solution, amounting to sulfuric acid 20-30 g/l Chloride can be added in proportions that supports the chloride content at the level of 12 g/l, as in the processing of copper concentrates. Conditions of carrying out the oxidation under pressure, i.e., temperature, pressure, etc., are also similar to the processing of copper concentrates. Cobalt is dissolved together with Nickel.

A solution of the product of the oxidation under pressure is first subjected to solvent extraction of copper by solvent where it removes almost all of the copper and then Nickel after re-heating up to 85-90oWith the precipitated basic Nickel sulfate, adding a solution of the limestone. Cobalt is deposited with the Nickel in the form of basic cobalt salt.

Then besieged basic sulphates of Nickel and cobal the obtained Nickel - and cobalt containing solution removed the cobalt by extraction of cobalt special cobalt extractant, such as Sapeh 272, which phosphinic acid, sold under the trademark Cyanamid company Inc. Then from the removal of cobalt raffinate extract Nickel, conducting extraction of Nickel by solvent using a different extractant, LIX 84 - hydrooxide sold under the trademark of Henkel Corp.

Finally, the raffinate obtained by removal of Nickel, recycle on stage leaching of Nickel and cobalt. Some portion of the raffinate is selected and processed for the extraction of ammonium sulfate, which otherwise accumulates in the loop. This is due to the introduction of sulfate ions in the solid filtered product of the basic sulphate of Nickel. To compensate the loss of ammonia in the ammonium sulfate should be added ammonia.

Nickel-copper concentrates

In the Nickel-copper concentrates predominant component is Nickel (8-25%), the copper content is about 3-10%. Technological scheme of this variant of the method shown in Fig. 6. Conditions of carrying out the oxidation under pressure is almost the same as in the processing of copper-Nickel concentrates. Where this differs from that presented in Fig. 5 deals with handling suspension produtora similar to mode a, where most of the copper after oxidation under pressure passes into the solid phase. To do this, prior to filtration of a suspension of the product of the oxidation under pressure in it add limestone to increase the pH to approximately 4. The result is the neutralization of the excess acid in the solution of the oxidation product under pressure, the deposition of iron in any form, and the deposition of copper in any form.

After neutralization, the suspension is filtered, and the solid precipitate filtered and sent to the atmospheric leaching, marked on the diagram as "leaching of copper", which receive the copper solution suitable for the extraction of the copper solvent.

The neutralized solution process, precipitating the Nickel and cobalt, and the extraction is carried out with a solvent scheme similar to that used for copper-Nickel concentrates.

Nickel laterite ore

Nickel laterite ore not beneficiated by flotation, as sulphide ores, so they must be treated together with waste rock. Typically, the Nickel content of these ores is from 1.5 to 3.0%, the content of cobalt is 0.1 to 0.3%, and the content of copper is negligible. It is important is to participate a significant amount of iron. Technological scheme of processing of laterite ores is shown in Fig. 7.

This method is similar to method used in the processing of Nickel-copper sulfide concentrates, except that the negligible content of copper in the ore, you can direct the solid residue from the leaching and neutralization in the blade. The method of processing laterite ores has some important differences regarding the conditions of the oxidation under pressure, namely, a much higher temperature and excess oxygen partial pressure is 225oWith and 3.1 MPa (450 psi), respectively, and much higher acidity of input solution corresponding to the content of free acid in the solution is equal to 100-200 g/l chloride Content remains the same - about 12 g/L. Chloride may be added to the solution in the form of magnesium chloride MgCl2or hydrochloric acid Hcl.

Another main difference of the method of processing lateritic ores is to remove magnesium. Magnesium in the oxidation under pressure leached into solution almost completely, usually for one cycle of leaching magnesium content in the solution is increased to 40 g/l Magnesium can be removed by evaporation of the and from the ore or concentrate, including the oxidation of the ore or concentrate under pressure at elevated temperature in the presence of oxygen and an acidic solution containing sulfuric acid or a sulfate of the metal, hydrolyzable in acidic solution, to obtain the solution of the recoverable metal, characterized in that the oxidation under pressure is carried out at 130-250oIn the presence of acid solution, optionally containing halogen ions.

2. The method according to p. 1, characterized in that when used as a feedstock deleterious ore oxidation under pressure is carried out at 130-150oC.

3. The method according to p. 1, characterized in that the oxidation under pressure is carried out at the total pressure of oxygen and steam, comprising 690-1380 kPa.

4. The method according to any of paragraphs. 1-3, characterized in that the halogen is selected from chlorine or bromine.

5. The method according to p. 4, characterized in that the oxidation under pressure is carried out in the presence of chloride ions with a concentration of 8 to 20 g/L.

6. The method according to p. 5, characterized in that the oxidation under pressure is carried out in the presence of chloride ions with a concentration of 12 g/L.

7. The method according to any of paragraphs. 1-3, 5 or 6, characterized in that the extracted metal is Nickel, and dopolnyayut from solution by the precipitation from this solution, Department of Nickel-containing precipitate from solution and leaching of Nickel from Nickel-containing precipitate to obtain a solution of a Nickel.

9. The method according to p. 1, wherein the ore or concentrate contains copper, which is leached into solution during the oxidation under pressure, and before the deposition of Nickel and copper are removed from the solution.

10. The method according to p. 9, characterized in that the copper is removed by solvent extraction.

11. The method according to p. 9, characterized in that the copper is removed by precipitation.

12. The method according to any of paragraphs. 1-3, 5 or 6, characterized in that the extracted metal is cobalt, and additionally carry out the selection of cobalt from solution.

13. The method according to p. 12, characterized in that the cobalt is recovered from solution by precipitation from this solution, separation of the cobalt containing precipitate from solution and leaching of cobalt from cobalt containing precipitate to obtain a solution of cobalt.

14. The method according to p. 1, wherein the ore or concentrate contains copper, which is leached into solution during the oxidation under pressure, and before the deposition of the cobalt copper is removed from solution.

15. The method according to p. 14, characterized in that the copper is removed extracts the manual according to any one of paragraphs. 1-3, 5 or 6, characterized in that the extracted metals are Nickel and cobalt, and optionally perform allocations of Nickel and cobalt from solution.

18. The method according to p. 17, characterized in that the Nickel and cobalt is recovered from solution by precipitation from this solution, the separation of Nickel and cobalt containing precipitate from solution and leaching of Nickel and cobalt from Nickel and cobalt containing precipitate to obtain a solution of Nickel and cobalt.

19. The method according to p. 17, wherein the ore or concentrate contains copper, which is leached into solution during the oxidation under pressure, and before the deposition of Nickel and cobalt copper is removed from solution.

20. The method according to p. 19, characterized in that the copper is removed by solvent extraction.

21. The method according to p. 19, characterized in that the copper is removed by precipitation.

22. The method according to p. 17, characterized in that it further carry out the selection of Nickel and cobalt from solution by selective solvent extraction to obtain separate solutions of Nickel and cobalt, suitable for electrochemical extraction.

 

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The invention relates to methods for extracting rare earth elements (REE) from acidic solutions with low initial content of REE and can be used for complex processing of phosphate raw materials, in particular the recovery of REE from leaching solutions phosphogypsum acids from solutions obtained by anatomisation decomposition of phosphate rock

The invention relates to ferrous metallurgy and can be used in the purification of zinc sulfate solutions obtained by metallurgical processing sulphide and oxide materials

The invention relates to hydrometallurgy of non-ferrous metals and is intended for extraction of valuable components from raw ore and mostly from low-grade ores, non-metallic rock, pulverized waste and (or) other industrial products and materials containing metals, their oxides, sulfides

The invention relates to metallurgy and can be used in the processing of polymetallic sulfide materials containing zinc, copper and iron
The invention relates to a method of purification of waste solutions from the Nickel ions and can be used for extraction of metallic Nickel from spent acid hypophosphite solutions of the chemical Nickel plating
The invention relates to a method of purification of waste technological solutions from Nickel ions and can be used for extraction of Nickel from spent alkaline solutions chemical Nickel plating containing ammonia

The invention relates to methods for processing of spent silver catalysts with obtaining pure silver or solutions of its compounds suitable for the preparation of catalysts

The invention relates to a method of recovering Nickel in one process of the two received pyrometallurgical methods Nickel mattes, one of which contains a significant percentage of iron

FIELD: autoclave hydrometallurgy, in particular hydrometallurgical reprocessing sulfide concentrates.

SUBSTANCE: method for reprocessing of sulfide concentrates with high content of pyrrotine includes blending of raw concentrate with mineral stabilizing additive; autoclave oxidative leaching of produced mixture in aqueous pulp under oxygen pressure at temperature above the sulfur melting temperature in presence of surfactant to convert non-iron metals into solution, sulfur - to elementary form, iron - to oxides; deposition of non-iron metal sulfides from oxidized pulp solution followed by recovery of non-iron metal sulfides and elementary sulfur by flotation into multiple sulfur-sulfide concentrate and iron oxides into rock refuse. Alkali or alkali-earth compounds with aluminum silicate are used as stabilizing additive, added at mass ratio of pyrrotine to total silica and alumina content of 1:(0.05-0.33) and mass ratio of copper to pyrrotine <1:55; or at mass ratio of pyrrotine to total silica and alumina content of 1:(0.5-0.8) and mass ratio of copper to pyrrotine 1:55 or more. Pyrrolitine decomposition ratio is at least 95 %, and leaching yield of sulfide mass is not less than during treatment of common pyrrotine concentrate.

EFFECT: improved method for reprocessing of sulfide concentrates.

9 cl, 1 tbl, 4 ex

FIELD: autoclave metallurgy of fused copper-nickel sulfide materials used in reprocessing of copper-nickel mattes and Bessemer mattes.

SUBSTANCE: claimed method includes oxidative atmospheric leaching of grinded material with reversible copper-containing solution from autoclave refining of copper product at elevated temperature and with pulp aeration with oxygen-containing gas for partial nickel conversion into solution and simultaneous copper deposition. Nickel solution is separated from iron and cobalt followed by electroextraction nickel isolation to produce nickel cathodes and reversible nickel anodic liquor. Solid residue from atmospheric leaching is oxidative leached in autoclave under excessive oxidative gas pressure by using copper and sulfuric acid-containing solution. Formed copper product is separated in autoclave from nickel, cobalt and iron with copper sulfate solution at elevated temperature and excessive water steam pressure to produce pulp used in isolating copper by common methods sulfide concentrate collecting platinum group metals and reversible copper-containing solution for atmospheric leaching of raw material. Oxidative atmospheric leaching is carried out using platinum electrode and silver chloride reference electrode at pulp redox potential of (+95)-(+245) mV, temperature of 90-118°C, partial oxygen pressure 0.08-0.25 MPa in presence of sodium sulfate and water-soluble iron ions in ratio iron/sodium sulfate in starting pulp solution of (0.002-0.035):1. Starting mass ratio of copper ions in pulp solution and nickel in solid residue from atmospheric leaching is maintained at (0.02-0.15):1. As sulfate solution for oxidative leaching in autoclave reversible nickel anodic liquor with addition of predetermined copper ion amount is used. Sulfate solution containing copper and sulfuric acid is obtained by addition in reversible nickel anodic liquor calculated amount of copper-containing solution.

EFFECT: copper sulfide concentrate with decreased nickel and iron content; simplified and lower cost equipment; reduced sulfur conversion into solution.

5 cl, 1 tbl, 3 ex

FIELD: metallurgy; complex processing of copper concentrate.

SUBSTANCE: proposed method includes sulphatizing roasting of starting concentrate and leaching-out of cinder at separation of metals; sulphatizing roasting of starting copper concentrate is performed in air at temperature of 500-600°C continued for 980-180 min; cinder thus obtained is leached-out with sulfuric acid solution or water at separation of cake and filtrate; copper is extracted from filtrate by electrolysis. Dried cake is blended with oxidizing agent and chlorides of alkaline and alkaline-earth metals and is subjected to heat treatment at temperature of 450-550°C for obtaining the cake which is leached-out by hydrochloric acid; noble metals are separated from filtrate by sorption method.

EFFECT: enhanced efficiency of extraction of metals; reduced power requirements; enhanced ecological safety.

9 cl, 1 dwg, 1 tbl, 3 ex

FIELD: hydro-metallurgy; reworking iron cakes containing non-ferrous metals, nickel and cobalt in particular; utilization of by-products of hydro-metallurgy for return of valuable components to technological process.

SUBSTANCE: moist cake is subjected to treatment with sulfuric acid in presence of ferric chloride (III) introduced in the amount of 4.5-7.5 mass-% of FeCl3 relative to Fe2O3 contained in pulp. Then, iron is reduced to bivalent state by sodium sulfite solution at concentration of 150-260 g/l at mass ratio of Fe2O3:Na2SO3=(0.18-0.23):1 at simultaneous deposition of iron in form of ferric sulfite (II) which is subjected to thermolysis in boiling mode continued for 0.5-1.5 h for forming hydrated ferrous oxide (II) which is separated from solution by filtration containing ions of non-ferrous metals; then, it is washed and subjected to heat treatment at 400-440°C for 0.5-1.5 h for forming ferric oxide (III). Thermolysis of ferrous oxide (II) may be performed under rarefaction; sulfur dioxide separated at this is neutralized with soda for obtaining sodium sulfite solution which is directed to iron reduction stage. Ferric chloride (III) solution may be obtained through treatment of part of iron cake in the amount of 3.5-5.5 mass-% of concentrated hydrochloric acid taken in stoichiometric amount relative to iron contained in cake. Proposed method makes it possible to increase extraction of non-ferrous metals iron cake to 96.5-98.5% at simultaneous obtaining ferric oxide (III) powder possessing pigment properties at reduced content of admixtures of non-ferrous metals.

EFFECT: facilitated procedure.

6 cl, 6 ex

FIELD: metallurgy; hydrochemical methods of a complex processing of a multicomponent, polymetallic scrap.

SUBSTANCE: the invention is pertaining to the field of metallurgy, in particular, to the hydrochemical methods of a complex processing of a multicomponent, polymetallic scrap used in nonferrous metallurgy with extraction of valuable components and production of various commercial products. The technical result at reprocessing and neutralization of wastes of production of titanium tetrachloride consists in concentration of radioactive metals in the "head" of the process, transfer of the secondary wastes of production in an ecologically secure form suitable for a long-term entombment and-or storing, as well as in production of an additional commercial products - deficient and expensive black thermo- resistant inorganic pigments based on iron oxides, manganese and copper oxides. The method provides for a discharge of the spent melt of titanium chlorates into water; concentrating of a pulp by circulation; the pulp thickening; settling of metals oxyhydrates from the clarified solutions in succession in three stages: on the first stage - conduct a settling at pH = 3.-5.0 with separation of the formed settling of hydroxides of chrome, aluminum and scandium from the solution; on the second stage - conduct settling at presence of an oxidizing agent at pH = 2.5-3.5 within 20-50 hours with separation of the settling; on the third stage - conduct settling at pH = 9.5-11.0. The pulp at its circulation and concentration is added with sodium sulfite in amount of 5 - 15 g/dm3, then after circulation the pulp is treated with a solution of barium chloride in amount of 10-20 g/dm3 for cosettling of ions of thorium and radium, in the formed pulp of the first stage of settling introduce a high-molecular flocculant, and before settling process on the third stage of the process the solution is previously mixed with copper(II)-containing solution formed after lixiviation of a fusion cake of the process of cleanout of the industrial titanium tetrachloride from vanadium oxychloride by copper powder, then the produced settling of iron, manganese and copper oxyhydrates is filtered off, cleansed, dried and calcined at the temperature of 400-700°C.

EFFECT: the invention allows to concentrate radioactive metals in the "head" of the process, to transfer the process secondary wastes in the ecologically secure deficient and expensive black thermo-resistant inorganic pigments.

5 cl, 1 ex

FIELD: extraction of zinc from zinc ore by means of halogenide-based leaching-out solution; removal of manganese from halogenide solutions of zinc and other metals.

SUBSTANCE: extraction of metallic zinc from zinc mineral includes the following stages: leaching-out of zinc mineral with solution containing halogenide compound of two or more halogenides, electrolysis of solution for obtaining metallic zinc and generation of halogenide compound and return of electrolyzed solution containing halogenide compound to leaching-out stage. Part of electrolyzed solution may be removed in form of flow escaping from cathode section of electrolyte cell of electrolysis process and may be treated for removal of manganese in form of manganese dioxide by addition of limestone and halogenide compound from anode section of electrolysis process. In this case pH and Eh of solution may be controlled by method enhancing formation of sediment of manganese dioxide as compared with formation of zinc sediment. Proposed method is characterized by low operational and capital outlays as compared with well-known methods, extraction of noble metals from solutions, tolerance to low-grade and contaminated concentrates.

EFFECT: reduced power requirements; avoidance of emission of liquid and toxic gases; low temperature and atmospheric pressure in carrying-out operations.

20 cl, 4 dwg, 6 tbl, 9 ex

FIELD: chemistry of organophosphorus compounds, chemical technology.

SUBSTANCE: invention relates to novel compounds used for extraction of rare-earth metal ions and comprising phosphoneamide compound represented by he formula [1]: wherein R1 means aryl group, aralkyl group under condition that each group can comprise a substitute chosen from alkoxy-groups; R2 means alkyl group, alkenyl group, aryl group, aralkyl group under condition that each group can comprise a substitute chosen from alkyl groups, alkoxy-groups; R3 means hydrogen atom, aryl group, aralkyl group under condition that each group can comprise a substitute chosen from alkyl groups, alkoxy-groups, halogen atoms; and two radical R can be combined to form alkylene group. Also, invention relates to a method for extraction of rare-earth metal ions and to a method for reverse extraction of rare-earth metal ions. Invention provides preparing novel phosphoneamide compounds and method for extraction and reverse extraction of rare-earth metal ions.

EFFECT: improved preparing method, valuable properties of compounds.

3 cl, 4 tbl, 44 ex

FIELD: chemistry.

SUBSTANCE: method for rhenium isolation implies passing rhenium-containg solution through strongly-basic anion-exchange resin and elution of adsorbed rhenium with high-concentration aqueous solution of hydrochloric acid. Anion-exchange resin is treated with an oxidising aqueous solution, where hydrogen peroxide is used as an oxidiser.

EFFECT: increase in ion exchanger service life.

10 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention rests on capability of metal ions to be extracted in stratified system of water, ammonium chloride, polyethyleneglycol ethers of synthetic fatty acid monoethanolamides (sintamide-5) of the general formula CnH2n+1CONH(CH2CH2O)mH (n=10-16; m=5-6) at the following component ratio, in mass %: ammonium chloride - 2-25; sintamide-5 - 5-45; water - up to 100.

EFFECT: quantitative extraction of thallium and gallium ions from water solutions without use of highly inflammable and toxic substances.

1 tbl, 2 dwg, 2 ex

FIELD: metallurgy.

SUBSTANCE: invention concerns manufacturing of radionuclides for industry, science, nuclear medicine, especially radioimmunotherapy. Particularly it concerns method of receiving actinium -227 and thorium -228 from treated by neutrons in reactor radium-226. Method includes irradiation of target containing of metallic capsule in which there is located reaction vessel, containing radium-226 in the form of compound. Then it is implemented unsealing of target's metallic capsule, dissolving of received radium. From solution it is separated by means of precipitation, and then it is implemented regeneration, preparation to new irradiation and extraction of actinium-227 and thorium-228 from solution. At that irradiation, dissolving, radium separation, its regeneration and preparation to new irradiation are implemented in the form of its united chemical form - radium bromide, in the same reaction vessel made of platinum. Method provides reusing of the same platinum vessel for receiving of actinium-227 and thorium-228 from one portion of radium by recycling of irradiation and extraction in the same vessel. Separation of metallic capsule by means of dissolving provides saving of mechanical integrity of platinum reaction vessel for each new irradiation cycle and extraction.

EFFECT: increasing of radiationally-environmental safety of process, excluding operations of increased radiation hazard.

2 cl, 2 ex

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