Method of joint separation of platinum metal

FIELD: metallurgy.

SUBSTANCE: invention relates to hydrometallurgy, particularly it relates to method of joint separation of platinum metal (PM). Method includes several stages: first stage is implemented for leaching of initial material, containing PM and impurity element. The second stage is implemented for removing of impurity elements from alkaline solution from leaching by solvent extraction, the third stage - for removing of palladium from raffinate. The fourth stage is implemented for removing from raffinate of impurity element cations by extraction by dissolvent. The fifth stage is implemented for extraction from the raffinate of platinum by hydrolysis, the sixth stage - for extraction from ruthenium settling by leaching and the seventh stage - for extraction of iridium by solvent extraction with receiving of desorbed alkaline solution, containing iridium, and raffinate containing rhodium.

EFFECT: effective removing of impurity elements, with each of separated PM allows grade enough for that it could serve in the capacity of commercial product.

18 cl, 14 tbl, 1 ex, 3 dwg

 

PREREQUISITES FOR CREATING INVENTIONS

The SCOPE of the INVENTION

The present invention relates to a method for simultaneous separation of platinum group metals (PGM), in particular to a method for simultaneous separation of PGMs from the source material, which also contains impurity elements in which to effectively remove impurity elements are highly stable compounds and certain stages and also prevents the increase in the content of impurities in the mother solution with respect to the content of PGM and, in addition, prevents the decomposition of the chloride complex, palladium, platinum, iridium, ruthenium and rhodium is separated together in such way that each of the separated PGM has a degree of purity sufficient to allow it to serve as commercial product.

DESCRIPTION of the PRIOR

Natural reserves of PGMs are rare and processing of natural minerals, such as platinum ores containing these metals at high concentrations is limited. The source materials for the production of these metals on a commercial scale are mostly by-products from the refining of non-ferrous metals, such as copper, Nickel and cobalt, and various exhaust catalysts, such as those used in the processing of the exhaust and the car gas.

By-products from the refining of non-ferrous metals contain PGMs, such as platinum, palladium, iridium, rhodium, ruthenium and osmium, are present in rathinasamy source materials in trace quantities. They concentrate due to their chemical properties in sulfide concentrates and unrefined base metals, such as copper and Nickel. They separated in the form of a concentrate of precious metals containing these metals as a residue from the extraction method of the base metal, such as electrolysis.

The concentrate typically contains, in addition to copper and Nickel as major metals, other components, such as noble metals (e.g. gold and silver), elements of the 16th group (for example, selenium and tellurium), and 15-th group (e.g., arsenic)that are present at higher concentrations than PGM. After the extraction of gold and silver should extract PGMs, which are separated from the residue containing these metals, together with impurity elements. Commercial way to separate/extract PGM from containing the above-mentioned starting material typically includes the leaching solution and the subsequent separation process, for example, by solvent extraction or adsorption, whereby a joint is separated and then rafinuyut.

Have been proposed or implemented several pic is of a scale, which IPY together separated and rafinuyut, and such methods and their inherent problems are disclosed in this specification.

Ways to separate PGM containing from their source material on a commercial scale can be represented in one way, based on, for example, in the following stages (a)-(g), carried out in the specified order, using as the main methods of separation solvent extraction:

(a) source material containing PGM leached water or chlorine with a receipt containing aqueous solution,

(b) the resulting aqueous solution is heated in the presence of nitric acid or similar compound as oxidant for distillation, osmium,

(C) the remaining solution was neutralized to obtain a slightly acidic environment and is heated in the presence of hydrochlorate sodium, chlorine or similar substances as oxidant for removal of ruthenium,

(d) the remaining solution is treated to increase the concentration of hydrochloric acid up to about 3 mol/l and lead in contact with simple debutalbum ether of diethylene glycol for the selective extraction of gold,

(e) the resulting raffinate is brought into contact with a moderately water-soluble alkylsulfides for the extraction of palladium

(f) the resulting raffinate is treated for recovery of the ion iridium(IV) ion iridium (III) and lead in contact with tributyl phosphate extraction of platinum, and

(g) the resulting raffinate is treated for oxidation of ion iridium (III) ion iridium (IV) and again brought into contact with tributyl phosphate extraction of iridium, leaving the rhodium in the raffinate.

These methods based on solvent extraction include the following to be the problem:

(1) prevent the increase in the content of impurities in the mother solution on the content of the IPY

These methods are based on the General concept of selective separation of gold and PGM, leaving the other impurity elements in the mother solution. As a result, the content of impurities on the content of PGM as the process gradually increases. For example, the impurity elements are often present when the content is 10-100 times greater than the total content of rhodium and iridium in the raffinate discharged from the stage of separation of the rhodium/iridium, which is the final stage of the method, which makes refining these elements greatly inconvenienced. Therefore, removing the IPY, with a degree of purity sufficient to ensure that they could serve as a commercial product, requires a very complex way, increasing the number of required stages of refinement, and because the residual content of impurity elements is increased, the loss of IPY, the selected VM is CTE with impurity elements, increase and, consequently, the yield decreases.

When solvent extraction using, for example, as an extractant simple dibutylamino ether of diethylene glycol concentration of hydrochloric acid in the aqueous phase is usually supported at the level of 3 mol/l or less, this gold is selectively extracted, but other impurity elements extracted slightly and remain in the raffinate. In other words, the impurity elements other than gold, are separated from the IPY insufficient.

(2) the Use of highly stable compounds and certain stages

As a result of separation of ruthenium is obtained by distillation of the gaseous oxide of ruthenium (VIII), which is very explosive and chemically active with respect to the organic compound. So you want a system made of vysokogradientnogo material, for example quartz glass, which leads to an increase of investments.

Refining containing iridium desorbed liquor discharged from the final stage, usually based on the rehabilitation division using as a reducing agent chloride mercury (I) due to its high ability to the separation of iridium from other related IPY. However, it is problematic stage from the point of view surrounding the Reda.

(3) prevent the decomposition of the chloride complex of platinum group metals in the mother solution

Department of ruthenium by distillation is often combined with the extraction solvent. For this method it is important at the same time to neutralize all the liquid and after the stage of distillation to increase the concentration of free hydrochloric acid in the entire fluid. This will lead to increased consumption of reagents and in the same time to increase the volume of the system due to the increased largely fluid volume.

Each of PGM support in the form of a chloride complex, which is more suitable for solvent extraction than any other form, and is resistant to hydrolysis occurring due to a change in pH. However, in the above method, including neutralization and heating, there is a tendency to decomposition of the complex and the decomposed product is difficult to return back to original shape even in the presence of the newly added hydrochloric acid. As a result, the separation efficiency of PGM extraction will decrease.

On the other hand, for methods that use the sorbent, with a variety of sorbents and methods of their use. They can be represented by the following methods, each of which typically has one or more problems from a practical point of view.

(1) In the patent is Japan's No. 3291203 (pages 1 and 2) revealed, for example, a process involving the adsorption of a mixture of platinum group metals in the form of an aqueous solution to the chromatographic medium, such as glycometabolic, and subsequent elution of acid solution to separate the individual elements. This way peculiar to the practical problems arising from the very low adsorption capacity of the environment, which leads to a significant increase in the volume of the system to retrieve a unit mass of each element. When processing 2 ml of the original solution containing, for example, PGM at a concentration of 0.3 g/l, required a very large column with a diameter of 10 mm and a length of 300 mm

(2) In the Japan patent JP-A-2001-98335 (pages 1 and 2) is disclosed, for example, a process involving the adsorption of a mixture of platinum group metals in the form of an aqueous solution of a copolymer of ethylene and methacrylic acid, copolymer of oligoarthritis or glycidylmethacrylate and pentaerythritoltetranitrate and subsequent elution using as eluent hydrochloric acid containing an oxidizing agent, for the separation of rhodium and subsequent elution of hydrochloric acid containing a reducing agent for the separation of platinum and iridium. This can be achieved separation of iridium, the adsorption properties of which vary markedly when it is oxidized or restored, but it has practical problems in the t is odesta, occurs when the joint Department of metals other than PGM.

(3) In the Japan patent JP-A-9-203792 (pages 1 and 2) is disclosed, for example, a process involving the sorption of the mixture nitrosoureas complex anion of each PGM in the form of an aqueous solution on anion-exchange resin and subsequent elution thiourea, ammonia, or similar connection for step a separate PGM. However, this method is inherent practical problems arising from difficulties with the joint division of PGM to such an extent that each of the separated elements had a degree of purity sufficient to be able to serve as a commercial product, as they are in the form of microcomplex and similar to each other in chemical properties.

(4) In the Japan patent JP-A-2001-516808 (pages 1 and 2) is disclosed, for example, a process involving the extraction of a mixture of platinum group metals in the form of an aqueous solution of 4-methyl-2-pentanone for the Department of impurity elements, such as gold, tellurium and iron, passing the resulting solution through a medium consisting mainly of gel complex of methacrylic acid, after which establish the redox potential of 500 mV or concentration of hydrochloric acid from 5.5 to 6.5 mol/l, and carry out subsequent elution hydrochloric acid conc is of 6 mol/l for separating a mixture of iridium, rhodium and ruthenium, palladium, platinum and osmium, in that order. Although using this method you can make a separate branch of palladium, platinum and osmium, he has a problem with the need for a separate stage intended for separation of iridium, rhodium and ruthenium separated from the surrounding copper, bismuth, lead and arsenic as the main impurity elements, and also another problem that arises due to the significantly high content of impurity elements on the content of the IPY after separation of palladium and platinum as the main PGM. In addition, used in the first stage of this method as an extractant 4-methyl-2-pentanon largely lost during the process due to its very high solubility in water (19 g/l at 20C) and, in addition, it causes problems in relation to the environment due to its very low flash point equal to 17C.

In these circumstances there is a need in the ways of the joint Department of PGM from the source material, which also contains impurity elements, in which highly stable compounds (in terms of flash point and toxicity) and certain steps are used to improved the feasibility of the extraction solvent for the effective removal of impurity elements from odnovremennym to prevent the increase in the content of impurities in the mother solution with respect to the content of PGM and also prevent decomposition of the chloride complex, moreover, palladium, platinum, iridium, ruthenium and rhodium is separated together in such way that each of the separated PGM has a degree of purity sufficient to allow it to serve as a commercial product.

The INVENTION

The present invention is to provide a method for simultaneous separation/extraction of PGMs from the source material, which also contains impurity elements, in which, taking into account the problems with the traditional methods, to effectively remove impurity elements are highly stable compounds and certain stages and also prevents the increase in the content of impurities in the mother solution with respect to the content of PGM and, in addition, prevents the decomposition of the chloride complex, palladium, platinum, iridium, ruthenium and rhodium is separated together in such way that each of the separated PGM has a degree of purity sufficient to be able to serve as a commercial product.

After intensive research joint office of PGM from the source material, which also contains impurity elements, the authors of the present invention found that the above problem can be solved by the method of the present invention, comprising the successive stages of leaching with obtaining leaky p the current containing PGM solvent extraction using a specific extractant for the separation/removal of impurity elements, solvent extraction using a specific extractant for the separation/extraction of palladium solvent extraction using a specific extractant for the separation/removal of cations of impurity elements, hydrolysis to extract platinum separating the precipitate containing iridium, ruthenium and rhodium, leaching of sludge for separation/extraction of ruthenium and solvent extraction using a specific extractant for the joint office of iridium and rhodium, this effectively removes the impurity elements and palladium, platinum, iridium, ruthenium and rhodium is separated together so that each from isolated PGM has a degree of purity sufficient to allow it to serve as a commercial product.

The first aspect of the present invention is a method for simultaneous separation of PGMs from the source material, which also contains impurity elements, comprising the following stages:

(1) the first stage, during which a source material containing PGM leached in the presence of an oxidant while suspendirovanie in hydrochloric acid solution with obtaining liquor from the leaching containing the th IPY,

(2) the second stage, during which liquor from the leaching obtained in the first stage, separated by solvent extraction, representing a simple disutility ether of diethylene glycol, the organic phase containing the impurity elements, and the raffinate

(3) the third stage, during which obtained in the second stage, the raffinate is treated by solvent extraction, representing alkylsulfate, for the extraction of palladium, and the loaded solvent is then treated by the desorption of obtaining desorbed liquor containing palladium, and the raffinate

(4) the fourth stage, during which obtained in the third stage raffinate separated by solvent extraction, representing bis(2-ethylhexyl)phosphoric acid, the organic phase containing the cations of impurity elements, and the raffinate

(5) the fifth stage, during which obtained in the fourth stage raffinate hydrolyzing in the presence of an oxidant, and then bring the pH up to 5-12 obtaining sediment containing iridium, ruthenium and rhodium, and an aqueous solution containing platinum,

(6) sixth stage, during which obtained in the fifth stage of the leached residue in the presence of an oxidant in alkaline aqueous solution, supported at pH 12 or higher, to obtain the residue, containing iridium and rhodium, and liquor from the leaching containing ruthenium, and

(7) the seventh stage, during which obtained at the sixth stage, the residue is dissolved in hydrochloric acid to obtain an aqueous solution containing iridium and rhodium, the aqueous solution is treated by solvent extraction, representing tributyl phosphate, for extraction of iridium and then loaded solvent desorption process of obtaining desorbed liquor containing iridium and a raffinate containing rhodium.

The second aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which the oxidizer for the first stage is at least one selected from the group consisting of nitric acid, hydrogen peroxide and chlorine.

The third aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which the liquor from the leach to the second stage contains hydrochloric acid with a concentration of from 4 to 9 mol/L.

A fourth aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which each of the impurity elements in the organic phase of the second stage is at least one selected from the group consisting of an element that can form a lipophilic chloride complex, trivalent arsenic, which EurekAlert tetravalent selenium and tellurium.

The fifth aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which alkylsulfate for the third stage selected from the group consisting of dihexyl and dioctyladipate.

The sixth aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which the pH of the raffinate obtained in the second stage, the third stage before processing alkylsulfides is brought to a value from 0.5 to 2.5.

The seventh aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which the fourth stage is carried out at a pH from 2.5 to 4.5.

The eighth aspect of the present invention is a method for simultaneous separation of PGMs on the seventh aspect, in which as a pH regulator to use a salt of an alkali metal bis(2-ethylhexyl)phosphoric acid.

The ninth aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which the fifth stage is carried out at a temperature of from 60 to 100C.

The tenth aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which the fifth stage is carried out at a redox potential of from 100 to 700 mV, determined using as the electrode is a comparison of silver chloride electrode.

The 11th aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which the sixth stage is carried out at a redox potential of from 100 to 300 mV, determined using as a reference electrode of silver chloride electrode.

The 12th aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which the hydrochloric acid to the seventh stage contains hydrochloric acid at a concentration of from 3 to 7 mol/L.

The 13th aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which an aqueous solution containing iridium and rhodium, for solvent extraction on the seventh stage support when the redox potential of from 700 to 1200 mV, determined using as a reference electrode of silver chloride electrode.

The 14th aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which an aqueous solution for desorption at the seventh stage contains a salt of an alkali metal.

The 15th aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which to process liquor from the leaching with the sixth stage, the content is asego ruthenium, additionally included stage refining of ruthenium carried out in two stages: stage a recovery in the presence of a reducing agent with obtaining ruteniysoderzhaschim sediment and the degree of crystallization of obtaining crystal compounds of ruthenium dissolution of the precipitate.

The 16th aspect of the present invention is a method for simultaneous separation of PGMs on the 15th aspect, in which the degree of crystallization includes an aqueous solution ruteniysoderzhaschim precipitate is dissolved in hydrochloric acid combined with potassium chloride or ammonium chloride to obtain crystal compounds of ruthenium.

The 17th aspect of the present invention is a method for simultaneous separation of PGMs on the first aspect, in which processing of desorbed liquor with the seventh stage included stage refining iridium carried out in two stages: stage a recovery in the presence of metallic bismuth with obtaining an alloy containing PGM other than iridium, and an aqueous solution containing iridium, and the degree of crystallization with the receipt of an aqueous solution iridectomies crystal.

The 18th aspect of the present invention is a method for simultaneous separation of PGMs on 17-th aspect, in which the degree of crystallization includes originalarray aqueous solution, in advance of the Oka is slow in the presence of an oxidising agent and combined with potassium chloride or ammonium chloride to obtain iridectomies crystal.

Method for simultaneous separation of PGMs from the original material of the present invention, which also contains impurity elements through the use of highly stable compounds and certain stages may be applied to effectively remove impurity elements with simultaneous prevention of the increase in the content of impurities in the mother solution with respect to the content of PGM and prevention, in addition, decomposition of the chloride complex of the IPY, and the joint office of palladium, platinum, iridium, ruthenium and rhodium in such way that each of the separated PGM has a degree of purity sufficient to allow it to serve as a commercial product. This method, as such, has a very high industrial value.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 shows one example of the technological scheme of the method for simultaneous separation of PGM of the present invention.

Figure 2 shows one example of the technological scheme stage refining of ruthenium.

Figure 3 shows one example of the technological scheme stage refining of iridium.

LEGEND

1 - the First stage leaching of the source material containing PGM)

2 - Second stage (extraction solvent to remove impurity elements)

3 - the Third stage (extraction solvent for the extraction of palladium)

- The fourth stage (extraction solvent to remove cations impurity elements)

5 - the Fifth stage (hydrolysis of ruthenium, rhodium and iridium)

6 - the Sixth stage leaching of ruthenium)

7 - the Seventh stage (extraction solvent for extraction of iridium)

8 - Source material containing PGM

9 - hydrochloric acid Solution

10 - Oxidant

11 - the Residue from the leaching

12 - Simple disutility ether of diethylene glycol

13 - Organic phase containing impurity elements

14 - Alkylsulfate

15 - Desorbed liquor containing palladium

16 - Bis(2-ethylhexyl)phosphoric acid

17 - Organic phase containing the impurity cations of elements

18 - Oxidant

19 - Aqueous solution containing platinum

20 - Oxidant

21 - Liquor from the leaching containing ruthenium

22 - tributyl phosphate

23 - Desorbed liquor containing iridium

24 - raffinate containing rhodium

25 - stage refining of ruthenium

26 - stage refining of iridium

27 - Step recovery of ruthenium

28 - Re-leaching

29 - Re recovery of ruthenium

30 - Dissolution

31 - Crystallization of ruthenium

32 - Crystal compounds of ruthenium

33 - Step recovery iridium

34 - Stage crystallization iridium

35 - Precrystallization clean irit what I

36 - Originalarray crystal

37 - Alloy containing PGM other than iridium

DETAILED description of the INVENTION

Next, a method for simultaneous separation of PGM of the present invention are described in detail.

The method of the present invention is outlined with reference to figure 1, which shows one example of the technological scheme of the method for simultaneous separation of PGMs from the source material, which also contains impurity elements.

As follows from figure 1, the source material 8 containing the PGM process in the first stage 1 (leaching source material containing PGM), where its share leaching in the presence of an oxidant with 10 simultaneous suspendirovanie in hydrochloric acid solution 9 on liquor from the leaching containing PGMs, and the residue from the leaching of 11. Liquor from the leaching share in the second stage 2 (by solvent extraction to remove impurity elements) using as extractant simple dibutylamino ether of diethylene glycol 12 and the organic phase 13 containing impurity elements, and the raffinate. Obtained in the second stage raffinate share in the third stage 3 (extraction solvent for the extraction of palladium) using as extractant of alkylsulfate 14, after which the loaded solvent desorption process of obtaining on the sorbing liquor 15, containing palladium, and the raffinate.

Obtained in the third stage raffinate share in the fourth stage 4 (extraction solvent to remove cations impurity elements) using as extractant bis(2-ethylhexyl)phosphoric acid 16 in the organic phase, containing the cations of impurity elements 17, and the raffinate. Obtained in the fourth stage raffinate is treated at the fifth stage 5 (hydrolysis of ruthenium, rhodium and iridium), where it is hydrolyzed in the presence of an oxidising agent 18, and then bring the pH up to 5-12 obtaining sediment containing iridium, ruthenium and rhodium, and an aqueous solution 19 containing platinum.

Obtained in the fifth stage sediment share in the sixth stage 6 (leaching of ruthenium) leaching in the presence of the oxidizer 20 in strongly alkaline aqueous solution, supported at pH 12 or above on the residue containing iridium and rhodium, and liquor from the leaching of 21 containing ruthenium. Obtained at the sixth stage, the residue is dissolved in hydrochloric acid to obtain an aqueous solution containing iridium and rhodium, and share on the seventh stage 7 (extraction solvent for extraction of iridium), where the aqueous solution is treated with tributyl phosphate 22 for extraction of iridium and then loaded solvent desorption process of obtaining desorbed liquor 23, containing the th iridium, and the raffinate 24 containing rhodium.

Liquor from the leaching of 21 containing ruthenium, can be further processed at the stage of refining ruthenium 25 and therefore can be a desorbed solution 23 containing iridium, at the stage of refining iridium 26.

(1) the First stage leaching of the source material containing PGM)

In the first stage of the present invention leached source material containing PGM and impurity elements, in the presence of an oxidant while suspendirovanie in hydrochloric acid solution with obtaining liquor from the leaching containing PGM.

Subjected to the processing method of the present invention, the source material containing PGM and impurity elements is not limited. It can be a concentrate containing PGM and various impurity elements obtained from a by-product from the refining of non-ferrous metals, such as copper, Nickel and cobalt, or the spent catalyst of any type, such as used for treatment of automotive exhaust gases. Impurity elements include copper, Nickel, cobalt and iron as the main metals and other elements, such as gold, silver, lead, tin, selenium, tellurium, arsenic, antimony and bismuth.

Present in the source material specified PGM usually t is Auda metal or they are in the form of sulfide and can be dissolved in hydrochloric acid in the presence of an oxidant.

At this stage containing PGM material suspended in an aqueous solution containing hydrochloric acid, to which is added an oxidizing agent. Hydrochloric acid may be added to aqueous solution from the outset or, in the case when PGM is present in the form of a sulfide, it can be obtained chemically by the reaction of chlorine with sulfide and water. At this stage, most of the lead and silver related as impurity elements PGM usually remains as residue in the form of chloride, while others are dissolved in the form of chloride or chloride complex.

The oxidizing agent for this stage is not limited. He may be a nitric acid, hydrogen peroxide, chlorate, chlorite, hypochlorite, chlorine, bromate, hypobromite, bromine and peroxosulfates. However, for practical purposes, from the point of view of cost, preferably at least one compound selected from the group consisting of nitric acid, hydrogen peroxide and chlorine.

Conditions of leaching for a given stage is not limited. However, the selected conditions under which a strong chloride complex. For example, the temperature is preferably 70C. or higher and the concentration of hydrochloric acid in suspension equal to 4 mol/l or more. In other words, it is preferable to reliably turn each of PGM chloride in the set is the COP on the leaching step under the above conditions, to prevent hydrolysis at a later stage solvent extraction, which is bis(2-ethylhexyl)phosphoric acid.

(2) the Second stage (extraction solvent to remove impurity elements)

In the second stage of the present invention carry out the separation of the liquor from the leaching from the first phase by solvent extraction, representing a simple disutility ether of diethylene glycol, the organic phase is in the form of loaded solvent containing impurity elements, and the raffinate. Using this stage are removed mainly such impurity elements contained in the liquor from the leaching, which may form a lipophilic chloride complex, such as gold, tin, antimony, tellurium and iron. In addition, can also be extracted trivalent arsenic and tetravalent selenium. As a result, this stage can be effectively and collaboratively removed these impurity elements.

The concentration of hydrochloric acid at this stage is not limited, but preferably regulate in the range from 4 to 9 mol/L. At acid concentrations below 4 mol/l extraction of impurity elements other than gold, significantly slowed. On the other hand, when the acid concentration of more than 9 mol/l simple disutility ether detiling the Kohl overly eluted in the aqueous phase. Part of the IPY slightly extracted in the organic phase. However, they can be absorbed by the aqueous phase, washing the organic phase with an aqueous solution of hydrochloric acid of a concentration in the above range.

Extraction method extracted impurity elements from the organic phase is not limited. For the selective separation of gold and for the separation/removal of other impurity elements from the organic phase in the form of a precipitate of the hydroxide or basic salt can be used a known method desorption recovery aqueous solution of oxalic acid, sodium sulfite or similar compounds. In addition, you can also selectively remove the metal gold desorption with simultaneous separation of other impurity elements dissolved in the desorbed liquor, maintaining the pH at a value of 0.2 or less.

This method prevents an increased content of impurity elements in the mother solution with respect to the content of PGM, which is one of the problems with the traditional method of solvent extraction and solved by the present invention.

(3) the Third stage (extraction solvent for the extraction of palladium)

At the third stage of the present invention carry out the separation obtained in the second stage of the raffinate of the extraction solvent, PR is stablaudit alkylsulfate, for palladium extraction and subsequent processing by the desorption of the loaded solvent, obtaining desorbed liquor containing palladium, and the raffinate.

In this method as the extractant used alkylsulfate. Alkylsulfate is not limited, but as commercially available compounds preferred dihexyl or doctorsolve, with the first of these two is preferable. When using such a commercially available compound, it is necessary to carefully examine its selectivity for impurity elements.

Alkylsulfate is not limited, but is preferably diluted with a solvent-based hydrocarbon, so that it has a concentration of 10-50 vol.%. The extraction time is preferably 3 hours or more.

Obtained in the second stage, the raffinate is not limited by the pH value for the third stage, but before bringing into contact with alkylsulfides it is preferably adjusted to a value in the range from 0.5 to 2.5. Thus, it is possible to prevent the joint extraction of impurity elements, such as gold, selenium, antimony and tin, when they are present in the raffinate, which can occur when the specified phase extraction, solvent extraction, leaching or desorption formed by plating. When the pH value is below 0.5, the effect of preventing the possible joint extraction may be insufficient, that gives the possibility of impurity elements to be extracted together with palladium. On the other hand, when the pH value is higher than 2.5 may be precipitated bismuth, which will cause the joint deposition of PGM.

Moreover, at this stage can be precipitated tellurium, antimony and tin, when they are present in the raffinate from the second phase at a concentration of several tens of mg/L. If a precipitate, it is preferably separated in advance before the next stage.

When the concentration of the acid decreases, the regulation of the pH of the raffinate from the second stage makes it possible to reduce the solubility of simple dibutylamino ether of diethylene glycol, dissolved in solution, from 0,n ~ ng/l to 0.01 g/liter separates the simple disutility ether of diethylene glycol, which can be removed by flotation.

At this stage, the organic phase containing palladium, desorbed, for example, ammonia water to form a desorbed liquor containing palladium. For separation/removal related impurity elements in the organic phase before desorption preferably should be rinsed, for example, hydrochloric acid with a concentration from 1 to 2 mol/L. the Organic phase is recovered by desorption, re-used for the extraction step.

Palladium, having a degree of purity, eno is ing for so he could serve as a commercial product, is extracted from desorbed liquor containing palladium known method. So, for example, crystal chloride diamondblade (II) with purity of at least about 99.9 wt.% (in terms of metal) can be obtained by neutralization of the desorbed liquor hydrochloric acid.

(4) Fourth stage (extraction solvent to remove anions impurity elements)

In the fourth stage of the present invention carry out the separation of the raffinate from the third stage by solvent extraction, representing bis(2-ethylhexyl)phosphoric acid, the organic phase containing the cations of impurity elements, and the raffinate. At this stage, carry out the extraction/removal of cations of impurity elements such as bismuth, copper, lead and Nickel, which can not be separated/removed in the second stage.

At this stage, as the extractant used bis(2-ethylhexyl)phosphoric acid. In principle, this stage can be used any acid extractant. However, when it is less acidic (or has a higher pKa value)than bis(2-ethylhexyl)phosphoric acid, it is necessary to increase the pH value of the extraction of each metal ion, which can cause hydrolysis and precipitation of bismuth. On the other hand, when the it is more acidic (or has a lower pKa value), may be difficult desorption.

A solution of bis(2-ethylhexyl)phosphoric acid is not limited, but is preferably diluted with a solvent-based hydrocarbon, so that it has a concentration of 10-50 vol.%.

Obtained in the third stage, the raffinate is not limited by the pH value for the fourth stage, but it is preferably adjusted to a value in the range of from 2.5 to 4.5. When the pH value is below 2.5 extraction of impurity elements may be insufficient. On the other hand, when the pH value is higher than 4.5, bismuth, if present, may be precipitated, which can cause the plating.

Methods of regulation of pH for the fourth stage is not limited. However, it is preferable to use bis(2-ethylhexyl)phosphoric acid after it is partially converted into a salt of an alkali metal.

So, for example, preferably include the raffinate from the third stage, mixed with bis(2-ethylhexyl)phosphoric acid, its alkali metal salt as a means for regulating the pH. When as a means for regulating the pH instead of the alkali metal salt is used alkali bismuth, when it is present in the raffinate can directly interact with the alkali to obtain sediment oxychloride or the like. Stage extraction, including ion-exchange reaction between the alkali metal ion in the ion extractant and Rimskogo element, can prevent the deposition of compounds of bismuth.

The processing method of the organic phase with this stage is not limited but is preferably washed with an aqueous solution containing salt, close to neutral, for example sodium chloride before being processed by desorption. This allows physical eject droplets of water dispersed or suspended in the organic phase in the aqueous phase. In other words, the aqueous phase is physically dispersed or suspended in the organic phase, while the chloride complex PGM forming anion, remains extrahieren bis(2-ethylhexyl)phosphoric acid.

The method of processing the washed organic phase is not limited. It can be treated by the desorption of strongly acidic solution such as hydrochloric acid, nitric acid or sulfamic acid, a known method. When the organic phase contains as an impurity bismuth or lead, for efficient processing of the organic phase at low concentrations it preferably desorbed solution of hydrochloric acid, because it can form a complex with these elements. The concentration of hydrochloric acid solution for desorption is not limited, but preferably is in the range from 0.5 to 2 mol/L. At a concentration of less than 0.5 mol/l bismuth is the set obtained from receiving sediment. On the other hand, at a concentration of more than 2 mol/l solubility of chloride of lead can be reduced due to the common ion impact on the Department. Regenerated by desorption of the organic phase is re-used for the extraction.

At this stage, is achieved by preventing the increase in the content of impurities on the content of PGM in the mother solution, which is one of the problems with the traditional solvent extraction.

(5) Fifth stage (hydrolysis of ruthenium, rhodium and iridium)

At the fifth stage of the present invention to carry out processing of the raffinate from the fourth stage, while it is hydrolized in the presence of an oxidant, and then bring the pH up to 5-12 obtaining sediment containing iridium, ruthenium and rhodium, and an aqueous solution containing platinum. At this stage selectively allocated platinum in the form of a soluble in an aqueous solution of platinate alkali metal, whereas hydrolyzable ruthenium, rhodium and iridium can be easily separated in the form of hydroxide precipitation.

At this stage the pH of the raffinate from the fourth stage is brought to a value in the range of 5-12. When the pH value is less than 5 hydrolysis of ruthenium, rhodium and iridium may be insufficient. On the other hand, when the pH value is above 12 precipitated hydroxides of these elements can dissolve again. Means for regulating the pH to Dunn the stage is not limited as it uses water-soluble alkali. One of the preferred means is sodium hydroxide.

The temperature for this stage is not limited. When the temperature rises, the hydrolysis proceeds faster. In particular, the preferred temperature is from 60 to 100C. At temperatures below 60C, the hydrolysis can occur sufficiently. On the other hand, at temperatures above 100C. to perform the reaction requires autoclave reactor.

The redox potential for this stage is not limited, but preferably it is set at a value of from 100 to 700 mV, more preferably from 200 to 400 mV, determined using a silver chloride reference electrode. IPY is subjected to the first stage of the high-oxidizing environment and ruthenium, rhodium and iridium are transformed into tetravalent chloride complex. However, before the fifth stage after mixing with various solvents they are gradually recovering, sometimes to the trivalent state. For full deposition of ruthenium, rhodium and iridium, it is important to support each of them in the form of tetravalent hydroxide, which has a low solubility. When the redox potential of less than 100 mV, determined using a silver chloride reference electrode, oxidation PGM is insufficient for obtaining hydroxides of ruthenium, rhodium and iridium. the other hand, when the redox potential of more than 700 mW PGM can be partially oxidized to the hexavalent state and hydroxides dissolve. Moreover, the ruthenium can be oxidized even before osmislennogo state with the formation of RUO Li4which, as you know, is a volatile and explosive.

The oxidizing agent for this stage is not limited. He may be a chlorine, hypochlorite, chlorite, bromide, bromate, hypobromite or peroxosulfates that behaves effectively in the environment from neutral to alkaline. Of these oxidizing agents is preferred chlorite sodium, because it is easily stored, has a low speed samorazrusheniya in the process of reaction and low cost.

From the standpoint of overall efficiency of the process, at this stage it is important to improve the outputs of ruthenium, rhodium and iridium are contained at a lower content than platinum. When this stage is carried out at conditions which assure complete precipitation of ruthenium, rhodium and iridium, the coprecipitation of platinum is inevitable. However somadina platinum can be separated in the form of an aqueous solution at the subsequent stages of refining ruthenium, rhodium and iridium and completely removed by additional processing of the aqueous solution, for example the recovery of hydrazine hydrate as described below.

Platinum, which is the t of ruthenium, rhodium or iridium, can be extracted from the containing platinum aqueous solution by a known method so that it had a degree of purity sufficient to serve as a commercial product. For example, the crystal hexachloroplatinate (IV) ammonium with the degree of purity of at least about 99.9 wt.% (in terms of metal) can be obtained when an aqueous solution restore hydrazine hydrate dissolved in hydrochloric acid in the presence of an oxidising agent and combined with ammonium chloride.

(6) Sixth stage leaching of ruthenium)

In the sixth stage of the present invention carry out the separation of the precipitate from the fifth stage leaching in the presence of an oxidant in alkaline solution, supported at pH 12 or above on the residue containing iridium and rhodium, and liquor from the leaching containing ruthenium. At this stage, carry out the oxidation of the precipitate in alkaline aqueous leach solution of ruthenium in the form of ruthenate (VI) of sodium.

Strongly alkaline aqueous solution for a given stage is supported at pH 12 or above, preferably at pH 13 or higher. When sodium hydroxide is used for the above purpose, it is preferably in the form of at least 10 wt.% aqueous solution. Ruthenate (VI) sodium is more stable in solution with high Majesty is Noah pH. When the pH value is below 12 ruthenate (VI) sodium is formed to a small extent. Means for regulating the pH at this stage is not limited in its use of water-soluble alkali. One of the preferred means is sodium hydroxide.

The redox potential for this stage is not limited, but is preferably set in the range from 100 to 300 mV, determined using a silver chloride reference electrode. When redox potential below 100 mV, determined using a silver chloride reference electrode, a hydroxide of ruthenium (IV) can be sufficiently oxidized in ruthenate (VI) of sodium. On the other hand, when the oxidation-reduction potential higher than 300 mV, this stage can be inefficient due to excessive auto-oxidation of the oxidizing agent.

The oxidizing agent for this stage is not limited. He may be a chlorine, hypochlorite, chlorite, bromide, bromate, hypobromite or peroxosulfates, which is effective in an alkaline environment. Of these oxidizing agents is preferred chlorite sodium due to its easy storage, low speed samorazrusheniya in the process of reaction and low cost.

The concentration of the sludge in suspension for this stage is not limited, but preferably it is extending t is 100 g/l or less, more preferably from 10 to 100 g/l When the concentration of the slurry is reduced, the degree of leaching increases. When the concentration of the slurry of 100 g/l or less, it can usually be 90% or more.

To obtain ruthenium high purity degree of leaching of ruthenium intentionally support low to control the leaching of PGMs and impurity elements by regulating the conditions at this stage, such as redox potential, pH and concentration of the sludge.

Unlike the traditional way of separating ruthenium, at this stage it is possible to separate/extract ruthenium without the use of distillation and, therefore, to facilitate the implementation of the method for simultaneous separation of PGM using highly stable compounds.

(7) the Seventh stage (extraction solvent for extraction of iridium)

At the seventh stage of the present invention carry out the separation of iridium and rhodium. Iridium - and registergui balance with the sixth stage is dissolved in a solution of hydrochloric acid, the extraction is carried out with a solvent, which is used as tributyl phosphate, for extraction of iridium, then loaded solvent is subjected to desorption with getting desorbed liquor containing iridium and a raffinate containing rhodium.

The temperature at which the residue is dissolved in races is the thief of hydrochloric acid, not limited. However, it is preferably from 60 to 100C. When the heating is carried out at a temperature in the above range, iridium can be dissolved in the form of hexachloroiridium (IV) acid.

The concentration of hydrochloric acid to dissolve the residue is not limited, but preferably it ranges from 3 to 7 mol/l, for a given concentration, more preferably at a concentration of from 4 to 7 mol/l, iridium can be sufficiently extracted in the form hexachloroiridate (IV) acid.

The redox potential of containing iridium and rhodium aqueous solution for the above mentioned stages of the extraction solvent is not limited, but preferably it is placed in the presence of an oxidant at a value of from 700 to 1200 mV, more preferably from 800 to 1000 mV, determined using a silver chloride reference electrode. When the redox potential of less than 700 mV ion hexachloroiridate (IV) is unstable, it is partially reduced to trivalent iridium and cannot be sufficiently extracted in the organic phase. On the other hand, increasing the potential of 1200 mV does not contribute to increasing the degree of extraction.

The oxidizing agent for this stage is not limited. He may be a chlorine, chlorate, chlorite is, hypochlorite, bromate, Iodate, nitric acid, of which nitric acid is particularly preferred because it acts as a catalyst promoting the formation of a chloride complex PGM.

In the case where an aqueous solution, in addition to iridium and rhodium, contains ruthenium, it is preferably combined with the nitrite ion, due to the fact that it accelerates the formation of pentachloronitrobenzene (III) acid, ruthenium together with iridium extracted into the organic phase, thereby increasing the degree of purity of rhodium in the aqueous phase.

Used at this stage aqueous solution for desorption of the organic phase containing iridium, is not limited. He may be a water or a dilute acid having a concentration of 1 mol/l or less. Particularly preferred is an aqueous solution of water-soluble alkali metal salts, e.g. sodium chloride, because it prevents insufficient phase separation and hydrolysis of the impurity element in the organic phase.

For a more complete desorption of iridium and other elements, together present in the organic phase, is effective desorption in a reducing environment in the presence of an aqueous solution containing hydrazine, its connection, sulfurous acid or sulfite. However, it should be noted that the reducing agent suspended or dissolved in the organic phase, can reduce the redox potential of the solution during the extraction process. In this case, it is necessary to maintain the aqueous solution in the extraction step in the redox potential of 700 mV or more.

Rhodium having a degree of purity sufficient to allow it to serve as a commercial product, is extracted from registeruser of raffinate-known method. For example, it combines with sodium nitrite to obtain hexanitrate (III) sodium, dissolved in hot water for refining to remove impurities, and then combine with ammonium chloride for selection/extraction of crystalline hexanitrate (III) ammonium. He has a degree of purity equal to at least about 99.9 wt.%.

(8) stage refining of ruthenium

Method for simultaneous separation of PGMs present invention may include, if necessary, stage refining of ruthenium, which process liquor from the leaching containing ruthenium, with the sixth stage. Stage refining of ruthenium includes the steps of recovery and crystallization, and the first two of these steps includes the handling of liquor from the leaching containing ruthenium, a reducing agent with obtaining ruteniysoderzhaschim sediment and last (second) stage involves the dissolution of sieges is while obtaining crystal compounds of ruthenium.

Method of crystallization is not limited. However, the crystal is preferably obtained by inclusion of potassium chloride or ammonium in aqueous solution ruteniysoderzhaschim precipitate is dissolved in dilute hydrochloric acid. At this stage of the receive crystal compounds of ruthenium having a degree of purity sufficient to allow it to serve as a commercial product.

Figure 2 shows one example of the technological scheme stage refining of ruthenium. As follows from figure 2, at this stage of the process liquor from the leaching of 21 containing ruthenium, obtaining crystal compounds of ruthenium 32 in two stages: stage recovery of ruthenium 27 and the degree of crystallization, including the dissolution of 30 sediment obtained by reduction and crystallization 31. In addition, the precipitate obtained by reduction can then be treated, if necessary, re-leaching 28 and repeated recovery of ruthenium 29.

On the level of recovery this stage is present in the liquor from the leaching of ruthenate (VI) sodium containing ruthenium, is restored in the presence of a reducing agent in the hydroxide ruthenium (IV) in the form of sludge. When the liquor from the leaching of as an impurity is present platinum, it is allocated at this stage, mostly in the mother solution, and is subject to separation from Rute the Oia. For a more complete selection of platinum from the mother liquor preferably, the precipitate containing the hydroxide of ruthenium (IV), videlacele in the presence of alkali applying the methodology used for the sixth stage, and then again restored with obtaining a precipitate. Hydroxide ruthenium (IV) precipitates when the redox potential of about 0 mV, determined using a silver chloride reference electrode.

The reducing agent for this stage is not limited. It is preferably selected from a weak reducing agents, such as alcohols, ketones and sugars, which can selectively restore ruthenium.

On-stage crystallization of this phase of ruthenium hydroxide (IV) can be dissolved in hydrochloric acid in the form of hexachlororuthenate (IV) acid or its hydrated complex ion and then combined with potassium chloride or ammonium obtaining crystal hexachlororuthenate (IV), oxopentanoate (IV) or oxitetraciclina (IV). Even when other than platinum, the impurity element is present in trace quantities, it can be completely distributed in the mother solution. At this stage it is possible to obtain the crystal of ruthenium compounds with purity of at least about 99.9 wt.% (in terms of metal).

To obtain a more pure ruthenium on this study which can optionally if necessary, to effect recrystallization, during which the crystal can be restored with a weak reducing agent such as hydrazine-chloride or sulfite-ion, chloride, ruthenium (III) in the form of an aqueous solution, which is again oxidized by the oxidizing agent.

(9) stage refining iridium

Method for simultaneous separation of PGMs present invention may additionally include, if necessary, the stage of refining iridium, which process desorbed liquor with the seventh stage. Stage refining iridium includes the steps of recovery and crystallization, with the first of these two steps is carried out restoration desorbed liquor metallic bismuth with obtaining an alloy containing PGM other than iridium, and an aqueous solution containing iridium, and on the last (second) stage treated with an aqueous solution of obtaining iridectomies crystal.

Method of crystallization is not limited. However, the crystal preferably is produced by oxidation of iridium in an aqueous solution of oxidizing agent, and then switching in the solution of potassium chloride or ammonium.

Figure 3 shows one example of the technological scheme stage refining of iridium. As follows from figure 3, at this stage, carry out two-stage processing of desorbed liquor 23, steriade what about iridium, obtaining iridectomies crystal 36, including the step of recovery of iridium 33 and the degree of crystallization 34, and the first of these two steps get alloy 37, containing PGM, other than iridium, and an aqueous solution containing iridium, and on the last (second) stage of process aqueous solution. In addition, if necessary, may be included the step precrystallization cleaning 35 iridium.

The reducing agent for the degree of recovery at this stage preferably is a metal bismuth, because it can easily maintain the redox potential with a value of +300 mV, determined using a silver chloride reference electrode, in which the iridium ion is not restored, and the other IPY can be reliably restored. This fact gives an opportunity to obtain an alloy containing PGM, other than iridium, and an aqueous solution containing iridium.

On-stage crystallization of this phase an aqueous solution containing iridium, again combine with the oxidant to maintain the value of the redox potential of from 700 to 1000 mV, preferably from 800 to 1000 mV, determined using a silver chloride reference electrode. The result is an ion of hexachloroiridate (IV), which is required about what adowanie crystal. When the value of the redox potential of less than 700 mV ion hexachloroiridate (IV) is unstable and partially reduced to the trivalent state. On the other hand, when the value of the redox potential of more than 1000 mW of lead can go in the tetravalent state, although only to a limited extent, with the formation of hexachloroplatinate (IV), polluting isomorphic originalarray crystal.

The oxidizer stage of crystallization is not limited. He may be a chlorine, chlorate, chlorite, hypochlorite, bromate, Iodate, or nitric acid.

In the degree of crystallization of an aqueous solution having the desired redox potential, then combine with potassium chloride or ammonium. In the iridium may crystallize selectively obtaining crystal hexachloroiridate having a purity of at least about 99.9 wt.% (in terms of metal).

To obtain a more pure compounds of iridium at this stage, if necessary, it is possible to additionally carry out the recrystallization of the crystal in which the crystal can be restored with a weak reducing agent such as hydrazine-chloride or sulfite-ion, iridium chloride (III) in the form of an aqueous solution, which is again oxidized by the oxidant. When the crystal hexachlor is ridata (IV) ammonium additionally rafinuyut by recrystallization, can be carried out oxidation/decomposition of a strong oxidant, for example, in the aquatic environment, in order to oxidize the ammonium ion in nitrogen and make it soluble. Moreover, can be formed isomorphic crystal hexachloroplatinate (IV), polluting the obtained crystal. However, it can be easily separated when recrystallized cleaner connection iridium, while the concentration of the crystalline slurry support at 100 g/l or less.

Used in the present invention for each stage of the extraction solvent has a flash point of 70C. or higher. The diluent for the present invention may be selected from commercially available hydrocarbons, such as alkyl benzenes, alkylnaphthalenes, alkylcyclohexanes etc., having a flash point of 70C or higher.

As discussed earlier, a joint office of the PGM of the present invention is the use of highly stable compounds and certain stages, making the problem inherent in the traditional methods using solvent extraction.

EXAMPLE

The present invention is described in more detail by example, and in no way limiting the present invention. Metals were analyzed in the sample using ICP-AES.

Example 1

Concentrate PGM used in which the quality of the source material, worked on the following sequential stages: leaching of material containing PGM (first stage), extraction solvent for removal of impurity elements (second stage), extraction solvent for the extraction of palladium (third stage), extraction solvent for the removal of cations of impurity elements (the fourth stage), hydrolysis of ruthenium, rhodium and iridium (fifth stage), the leaching of ruthenium (sixth stage) and ruthenium refining, solvent extraction for the extraction of iridium (seventh stage) and the refining of iridium. Researched products with these stages. Table 1 provides the chemical composition of the concentrate PGM was used as the source material. Part of each PGM was in the form of sulphide.

Table 1
PtPdRhIrENCuSePbBiSbTeSnAu
0,953,820,20 0,030,410,170,0815,213,70,040,130,011,45
(Unit: wt.% (in terms of wet matter))

(1) the First stage

The above concentrate PGM was videlacele chlorine, with 60 kg of concentrate suspended in 200 l of water and the resulting suspension after heating up to 80C have sealed chlorine and maintained for 3 hours at maximum redox potential 1050 mV (determined using silver chloride reference electrode, hereinafter in the description sometimes marked redox potential (ORP)). The obtained liquor from the leach became a hydrochloric acid solution with a concentration of 5 mol/l, as contained in the original concentrate sulfur interacted with chlorine. Processed by leaching the slurry was separated by filtration on liquor from the leach residue, which is washed with 30 l of water to obtain 280 l of liquor from the leaching (including wash water) and 13.5 kg of residue (moisture content: 4.2 wt.%). The residue was dried. In table 2 is given the chemical composition of each product.

Table 2
PtPdRhIrENCuSePbBiSbTeSnAu
Liquor from the
leach
g/l2,018,110,430,0580,880,40,163,4129,40,0390,270,012,95
Balancewt.%0,040,1430,010,0030,0180,0060,00663,5 <0,1<0,l<0,005<0,0050,32

(2) the Second stage

Obtained in the first stage liquor from the leach processed by solvent extraction to remove impurity elements using a multi-stage countercurrent mixer/settler and as an extractant simple dibutylamino ether of diethylene glycol (DBC). Conducted a two-stage extraction and three-stage leaching by hydrochloric acid with a concentration of 5 mol/l, where the ratio of liquor from the leaching/DBC/wash solution of hydrochloric acid was 1/0,25/0,25. Wash solution discharged from the stage of washing was combined with the stream flowing in the first stage of extraction. The mixing time and the time separation of the phases in each of the steps of extraction and washing was set equal to 10 and 20 minutes, respectively. In the extraction liquor from the leaching was divided into 350 l of raffinate and 87.5 l extracted organic phase. Analyzed the chemical composition of each product. The results are given in table 3.

Table 3
The products obtained by extraction DBC PtPdRhIrENCuSePbBiSbTeSnAu
The organic phase0,0570,0130,0150,0010,0590,0000,0010,0020,0040,1250,8450,0279,421
The raffinate1,59of 6.490,340,0460,690,300,132,7323,5<0,0010,005<0,0010,005

(Unit: g/l)

As shown in table 3, in the second stage produced the walks joint Department of antimony, tellurium, tin and gold as impurity elements.

The organic phase this phase was recovered aqueous solution of sodium sulfite, following the usual method, and the resulting metal component is restored and desirerable. The regenerated organic phase is re-used for extraction.

(3) the Third stage

The third stage was combined with 350 l of the raffinate from the second stage with 233 l 24 wt.% aqueous sodium hydroxide solution to bring its pH to 1 and the diluted solution 117 l of water to obtain 700 l of an aqueous solution. The resulting aqueous solution was treated as an initial solution by solvent extraction for the separation of palladium, and the extractant was vexille (Daihachi Chemical Industry, SFI-6R), diluted EAT Clean 7250 (Nikko Petrochemicals) up to 20 vol.%. The extraction was carried out by a single stage using a mixer/settler, and the duration of extraction was equal to 3 hours. The organic phase was washed with an aqueous solution of hydrochloric acid with a concentration of 0.5 mol/L. the Ratio of the original solution/solution SFI-6R/wash solution of hydrochloric acid was 1,0/0,5/0,1. Washed raffinate discharged from the stage of washing, not United with the stream flowing in the stage of extraction, but instead separated/extracted. As a result of extraction who was alocale 770 l of raffinate and 350 l of extracted organic phase. Analyzed the chemical composition of each product. The results are given in table 4.

Table 4
SFI-6RPtPdRhIrENCuSePbBiSbTheSnAu
The organic phase0,0266,450,002<0,0010,008<0,001<0,001<0,001<0,001<0,001<0,001<0,0010,005
The raffinate0,7130,0180,1540,0210,310,1340,058 1,2410,7<0,0010,002<0,001<0,001

(Unit: g/l)

As shown in table 4, the third stage is the selective separation of palladium. Palladium organic phase was treated with an aqueous solution of ammonia, following the usual method, and the formed metal component was isolated by desorption. The regenerated organic phase is re-used for extraction. Containing palladium desorbed liquor was neutralized with hydrochloric acid and extraction of the crystal chloride diamondblade (II) with purity of at least 99 wt.% (in terms of metal).

(4) the Fourth stage

In the fourth stage raffinate from the third stage processed by solvent extraction to remove the anions of impurity elements, where as the extractant used bis(2-ethylhexyl)phosphoric acid (Daihachi Chemical Industry, DP-8R), diluted EM Clean 7250 (Nikko Petrochemicals), 50 vol.%. The extraction was performed using a two-stage countercurrent mixer/settler, and the duration of extraction in each stage was 0.5 hours. In each stage used the sodium salt DP-8R supported in the first and second stages at pH of 2.7 and 3.5, with the NGOs.

Extracted organic phase is washed with sodium chloride solution with a concentration of 1 mol/l and then desirerable hydrochloric acid with a concentration of 2 mol/L. the Ratio of the original solution/solution DP-8R/solution type sodium DP-8R/wash solution of sodium chloride/hydrochloric acid was set equal to 1/0,5/0,2/0,7/0,7. Wash solution discharged from the stage of washing, not United with the stream flowing in the first stage of extraction, but instead separated/extracted. As a result of extraction was obtained 770 l of raffinate and 539 l extracted organic phase. Analyzed the chemical composition of each product. The results are given in table 5.

Table 5
The products obtained by extraction of the DP-8RPtPdRhIrENCuSePbBiThe
The organic phase0,001<0,001<0,001<0,001 0,0010,190,0021,5415,2<0,001
The raffinate0,7120,0180,1540,0210,3090,0010,0570,1650,0210,0021

(Unit: g/l)

As shown in table 5, in the fourth stage is the selective separation of copper, bismuth and lead, and almost complete separation other than PGM elements.

(5) the Fifth stage

At the fifth stage was treated raffinate from the fourth stage of hydrolysis of iridium, ruthenium and rhodium and separate them because of this platinum. The raffinate was heated up to 80C and using a 24 wt.% sodium hydroxide brought the pH to 7, and at the same time, using 12 wt.% sodium hypochlorite was established redox potential of 400 mV. It was supported at the indicated pH and ORP within 30 minutes and the precipitate was removed by filtration. As a result of hydrolysis received 2.5 kg sediment (in terms of wet matter) and 801 l stock solution. Analyzed the chemical composition of each product. The results are given in table 6.

Table 6The products of hydrolysisPtPdRhIrENCuSePbBiTheThe precipitatewt.%7,340,303,600,507,560,040,0074,060,50,052The mother liquorg/l0,3190,0040,006<0,0010,002<0,0010,044<0,001<0,001<0,00l

(Unit: g/l)

As shown in table 6, at the fifth stage is fully deposited other than platinum, MP and separated more than half of the platinum distribution in the filtrate.

The mother liquor was processed, using conventional methods, while platinum was restored hydrazine hydrate and the reduction product was dissolved in hydrochloric acid in the presence of an oxidant and then was combined with ammonium chloride to highlight crystal hexachloroplatinate (IV) ammonium with the degree of purity of at least about 99.9 wt.% (in terms of metal).

(6) the Sixth stage and the stage of refining ruthenium

In the sixth stage treated sludge from the fifth stage to leaching of ruthenium, while 2146 g (in terms of wet matter) of sediment suspended in 24,6 l 24 wt.% an aqueous solution of sodium hydroxide and using 12 wt.% hypochlorite AFP resulting suspension was set equal to 200 mV. It was heated to 60C, reducing the level of AFP. So to re-maintain the level of AFP in the value of 200 mV was combined with an additional quantity of hypochlorite and kept at the specified AFP for 3 hours. The suspension had a pH of 14. The suspension was filtered to obtain 54,2 l liquor from the leaching and 2075 g (in terms of wet matter) of the residue from leaching. Analyzed the chemical composition of each product. The results are given in table 7.

Table 7
Products, poluchenierazreshenija EN PtPdRhIrENCuSePbBiThe
Liquor from the leachg/l3,710,0790,140,0694,110,0090,0030,430,0060,030
Balancewt.%1,360,24of 5.060,570,65to 0.0320,0024,990,78<0,001

As shown in table 7, in the sixth stage was leached 94.3% of ruthenium.

Liquor from the leaching subjected to processing for refining ruthenium.

First 54,2 l liquor from the leaching combined with 41 ml of the of ethanol for recovering ruthenium (VI), that led to a decrease in its level of AFP from 119 to -63 mV. The resulting suspension was filtered to obtain 843,9 g (in terms of wet matter) of sediment containing as a main component of ruthenium hydroxide, and 54,2 l stock solution. Analyzed the chemical composition of each product. The results are given in table 8.

Table 8
The products obtained by reduction ENPtPdRhIrENCuSePbBiThe
The precipitatewt.%0,40<0,0010,540,26425,90,054<0,0012,720,039<0,001
The mother liquorwt.%the 3.65 0,0790,0570,028of 0.066<0,0010,0030,004<0,0010,030

As shown in table 8, in the recovery of ruthenium was deposited 98.4% of ruthenium and only 17% of platinum.

Then the precipitate from the stage of recovery combined with 830 ml of 24 wt.% an aqueous solution of sodium hydroxide and water to form a 1,65 l suspension. With the use of sodium hypochlorite AFP suspension was set equal to 100 mV and was heated to 60C, reducing the level of AFP. So to re-level maintaining the redox potential at 100 mV was combined with an additional quantity of sodium hypochlorite and kept at the specified AFP for 3 hours. Then the suspension was filtered and the obtained residue was washed with water. The result has been 2,37 l of a solution of the compound of ruthenium (filtrate and wash water) and trace amounts of residue. Analyzed the chemical composition of each product. The results are given in table 9.

Table 9
The products obtained by repeated leaching EN PtRhIrENCuPbBi
Liquor from re-leachg/l0,350,0850,02472,40,0030,0490,057
Balancewt.%0,761,2760,63614,00,136,690,057

Then liquor from the re-leaching combined with 23 ml of methanol, which resulted in a reduction of its level of AFP from 80 to -54 mV. The resulting suspension was filtered and the resulting residue was washed with water. The result has been 2,37 l stock solution and 722,3 g (in terms of wet matter) again restored hydroxide ruthenium (IV). Analyzed the chemical composition of each product. The results are given in table 10.

Table 10
The products obtained by repeated recovery ENPtRhIrENCuPbBi
Newly refurbished productwt.%0,0020,0170,00523,33<0,0010,0160,019
The mother liquorg/l0,3470,0340,011,158<0,001<0,001<0,001

Then 722,3 g (in terms of wet matter) again restored hydroxide ruthenium (IV) was dissolved in 2 l of hydrochloric acid and was heated at 90C for 3 hours. The resulting solution was combined with 250 g of potassium chloride and the precipitated crystal tetrachloroaluminate (IV) potassium was removed by filtration. The result has been crystal and mother liquor. Analyzed the chemical composition of each product. R. the results are given in table 11.

Table 11
Products
obtained by crystallization
EN
PtPdRhIrENCuSePbBiTheFeAs
Crystalppm<20<10<10<1025,1*<10<20<20<20<10<10<10
Crystal
the mother solution
g/l<0,001<0,00l0,040,0120,0580,002< 0,0010,0390,046<0,001<0,001<0,001

(*Unit: g/l)

As shown in table 11, there was obtained the compound of ruthenium with a degree of purity of at least about 99.9 wt.%.

(7) the Seventh stage and the stage of refining iridium

At the seventh stage first treated residue from leaching from the sixth stage to the joint office of iridium and rhodium, while 2075 g (in terms of wet matter) of the residue from the leaching of dissolved 3.1 l hydrochloric acid, combined with 160 ml of nitric acid to accelerate education chloride complex, and was heated at 90C for 3 hours to obtain 3,53 l of a solution containing iridium and rhodium. It analyzed for chemical composition. The results are given in table 12.

Solution as the initial solution was treated by solvent extraction for the extraction of iridium using a multi-stage countercurrent mixer/settler, carrying out three-step extraction and two-stage leaching, the extractant used tributyl phosphate (Daihachi Chemical Industry, TBP), and for washing hydrochloric acid with a concentration of 4 mol/L. the Ratio of the original solution/TBP/washing chlorotoluron the acid was set equal 1/1/0,5. Wash solution discharged from the stage of washing was combined with the stream flowing in the first stage of extraction. The original solution had the AFP 950 mV.

Washed extractant prototechno brought into contact with 4 wt.% aqueous solution of sodium chloride of the same volume for the implementation of the two-stage desorption, while the mixing time and the time separation of the phases for each step was set equal to 10 and 20 minutes, respectively. As a result of extraction was obtained from 5.29 l of raffinate and 3,53 l iridium desorbed liquor. Analyzed the chemical composition of each product. The results are given in table 12.

Table 12
The raw materials and products obtained by separating Ir/RhPtRhIrEN
The original solution7,9929,743,333,81
The raffinate0,0119,70,120,97
Desorbed liquor7,98 0,153,152,36

(Unit: g/l)

As shown in table 12, at the seventh stage received iridium desorbed liquor containing iridium, platinum and ruthenium, and rhodium concentrate as the raffinate, which is distributed rhodium.

Iridium desorbed liquor was subjected to the processing for separating/refining iridium.

First iridium desorbed liquor was combined with 0.6 l of hydrochloric acid and 350 g of the granules of metallic bismuth, heated to 90C., and stirred until the solution of the lowest level of AFP (300 mV). Then the particles of the alloy, restored bismuth, filtered together with the remaining metallic bismuth. In the recovery of bismuth got to 61.3 g (in terms of wet matter) of sediment and 4,14 l of filtrate. Analyzed the chemical composition of each product. The results are given in table 13.

Table 13
Products recovery BiPtRhIrEN
The precipitatewt.%45,91 0,8550,3812,66
The filtrateg/l<0,001<0,0012,630,13

(Unit: g/l)

Then the filtrate (liquor from the recovery of bismuth) was oxidized with sodium hypochlorite to the level of the redox potential of 900 mV and then combined with 360 g of ammonium chloride. The precipitated crystal hexachloroiridate (IV) ammonium was separated by filtration. The result has been 30,9 g crystal and 4.1 l of filtrate. Thus obtained crystal compounds of iridium analyzed for its chemical composition. The results are given in table 14.

Table 14
PtPdRhIrENCuSePbBiTheFeAs
Crystal connection Ir<10<10<10 34,9*360<10<10250<20<10<10<50
Ir-containing crystal obtained by recrystallization<10<10<1035,1*<10<10<10<10<20<10<10<50

Unit: ppm, unit for Ir(*) - wt.%

As shown in table 14, obtained at this stage crystal compounds of iridium cannot be cleaned to the degree of purity of 99.9 wt.% or more (in terms of metal) because of the presence as contaminants of ruthenium and lead. Therefore additional ropinirole by recrystallization. Crystal suspended in 550 ml of hydrochloric acid with a concentration of 1 mol/l was combined with hydrazine hydrate to reduce its level of AFP to 500 mV and dissolved in acid. It is then recrystallized in prisutstvuyuthie sodium, consequently the level of AFP was increased to 900 mV. In the fell of 30.6 g (in terms of wet matter) iridectomies crystal. It was analyzed for its chemical composition. The results are given in table 14.

As shown in table 14, as a result of recrystallization degree of purity iridectomies of the crystal was increased to 99.9 wt.% or more (in terms of metal).

Disclosed above method for simultaneous separation of PGMs present invention is suitable for processing concentrates or similar source materials containing PGM and impurity elements, such as by-products from the refining of non-ferrous metals (e.g. copper, Nickel and cobalt) and various waste catalysts (such as that used for treatment of automotive exhaust gases) and sent to the division of the jointly present IPY with simultaneous removal of impurity elements.

1. Method for simultaneous separation of platinum group metals (PGMs) from a source material containing impurity elements, comprising the following stages:
(1) the first stage, during which a source material containing PGM leached in the presence of an oxidant while suspendirovanie in hydrochloric acid solution with obtaining liquor from the leaching containing PGM
(2) the second stage, during which liquor from the leaching obtained in the first stage, separated by solvent extraction, representing a simple disutility ether of diethylene glycol, the organic phase containing the impurity elements, and the raffinate,
(3) the third stage, during which obtained in the second stage, the raffinate is treated by solvent extraction, representing alkylsulfate, for the extraction of palladium, and the loaded solvent is then subjected to desorption with getting desorbed liquor containing palladium, and the raffinate,
(4) the fourth stage, during which obtained in the third stage raffinate separated by solvent extraction, representing bis(2-ethylhexyl)phosphoric acid, the organic phase containing the cations of impurity elements, and the raffinate,
(5) the fifth stage, during which obtained in the fourth stage raffinate hydrolyzing in the presence of an oxidant, and then bring the pH up to 5-12 obtaining sediment containing iridium, ruthenium and rhodium, and an aqueous solution containing platinum,
(6) sixth stage, during which obtained in the fifth stage of the leached residue in the presence of an oxidant in alkaline aqueous solution, supported at pH 12 or higher, to obtain the residue, containing iridium and rhodium, and liquor from the leaching, soteriades is ruthenium, and
(7) the seventh stage, during which obtained at the sixth stage, the residue is dissolved in hydrochloric acid to obtain an aqueous solution containing iridium and rhodium, the aqueous solution is treated by solvent extraction, representing tributyl phosphate, for extraction of iridium and then loaded solvent is subjected to desorption with getting desorbed liquor containing iridium and a raffinate containing rhodium.

2. The method according to claim 1, wherein the oxidant for the first stage is at least one selected from the group consisting of nitric acid, hydrogen peroxide and chlorine.

3. The method according to claim 1, in which the liquor from the leach to the second stage contains hydrochloric acid with a concentration of from 4 to 9 mol/L.

4. The method according to claim 1, wherein each of the impurity elements in the organic phase of the second stage is at least one selected from the group consisting of elements that can form lipophilic chloride complex, trivalent arsenic, tetravalent selenium and tetravalent tellurium.

5. The method according to claim 1, in which alkylsulfate for the third stage selected from the group consisting of dihexyl and dioctyladipate.

6. The method according to claim 1, wherein the pH of the raffinate obtained in the second stage to the third stage, before processing alcalali the house is brought to a value from 0.5 to 2.5.

7. The method according to claim 1, in which the fourth stage is carried out at a pH from 2.5 to 4.5.

8. The method according to claim 7, in which as a pH regulator to use a salt of an alkali metal bis(2-ethylhexyl)phosphoric acid.

9. The method according to claim 1, in which the fifth stage is carried out at a temperature of from 60 to 100C.

10. The method according to claim 1, in which the fifth stage is carried out at a redox potential of from 100 to 700 mV, determined using as a reference electrode of silver chloride electrode.

11. The method according to claim 1, in which the sixth stage is carried out at a redox potential of from 100 to 300 mV, determined using as a reference electrode of silver chloride electrode.

12. The method according to claim 1, in which the hydrochloric acid to the seventh stage contains hydrochloric acid at a concentration of from 3 to 7 mol/L.

13. The method according to claim 1, in which an aqueous solution containing iridium and rhodium, for solvent extraction on the seventh stage support when the redox potential of from 700 to 1200 mV, determined using as a reference electrode of silver chloride electrode.

14. The method according to claim 1 in which the aqueous solution for desorption at the seventh stage contains a salt of an alkali metal.

15. The method according to claim 1, in which the processing liquor from above is Oceania with the sixth stage, containing ruthenium, optionally included stage refining of ruthenium carried out in two stages: stage a recovery in the presence of a reducing agent with obtaining ruteniysoderzhaschim sediment and the degree of crystallization of obtaining crystal compounds of ruthenium dissolution of the precipitate.

16. The method according to item 15, in which the degree of crystallization includes an aqueous solution ruteniysoderzhaschim precipitate is dissolved in hydrochloric acid combined with potassium chloride or ammonium chloride to obtain crystal compounds of ruthenium.

17. The method according to claim 1, in which processing of desorbed liquor with the seventh stage included stage refining iridium carried out in two stages: stage a recovery in the presence of metallic bismuth with obtaining an alloy containing PGM other than iridium, and an aqueous solution containing iridium, and the degree of crystallization with the receipt of an aqueous solution iridectomies crystal.

18. The method according to 17, in which the degree of crystallization includes originalarray aqueous solution, pre-oxidized in the presence of an oxidising agent and combined with potassium chloride or ammonium chloride to obtain iridectomies crystal.



 

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4 ex

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5 cl, 5 tbl, 11 ex

FIELD: metallurgy.

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1 ex

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9 cl, 1 tbl, 25 ex

FIELD: metallurgy.

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1 dwg

 // 2350667

FIELD: technological processes; metallurgy.

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EFFECT: higher efficiency of process.

2 cl, 1 ex

FIELD: metallurgy.

SUBSTANCE: it is implemented treatment of copper-nickel sulfide concentrate by fluoride and/or ammonium bifluoride at the temperature 165-210°C during 2-3 hours with forming of hard fluorination products and emission of ammonia gas and water vapor. Fluoride and/or ammonium bifluoride are used in amount 1.0-1.2 from stoichiometric with respect to overall content in copper-nickel concentrate of silicates and pyrrhotine. Hard fluorination products exposed to water leaching at the temperature 40-60°C and S:L=1:5-6 during 1-2 hours with transformation to residue nickel sulfide, copper, cobalt, platinum metal and magnetite, and into solution - fluorine-ammonium silicon saline, magnesium, iron, aluminium and calcium. Residue is separated from solution and exposed to magnetic separation with magnetite extraction. Received solution is neutralised by ammonia water till providing of pH 8-10 with regeneration of fluoride and/or ammonium bifluoride and receiving of residue of magnesium, iron, aluminium, calcium and silica hydroxides. In the capacity of ammonia water for solution neutralisation can be used ammonia gas and water vapors from the stage of raw materials fluorination. Formed ammonium fluoride and/or bifluoride are returned to raw materials treatment stage.

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5 cl, 1 dwg, 4 ex

FIELD: metallurgy.

SUBSTANCE: invention concerns treatment of hard gold-arsenic ores. Particularly it concerns antimonous sulphide ores and concentrates. Method includes without oxidising melting in smelting chamber with receiving of matte and slag melts and treatment of melting products by metallic phase. At that without oxidising melting is implemented continuously in circulating melted slag with out of melting products into settling chamber to interphase boundary slag - matte. Before melting circulating melted slag is separated from operating gases. For circulating it is used maximum separated from matte slag. Treatment of matte by metallic phase is implemented in continuous operation. Furnace for processing of hard gold -arsenic ores and concentrates includes smelting chamber. Furthermore, it is outfitted by recycling contour, containing of gas-lift unit with tuyeres and descending and ascending channels of melted slag, gas separating and settling chambers. Gas separating chamber is communicated with smelting chamber through bleed blowhole by means of channel for separation of working gas of gas-lift unit and gas separating chamber from circulating melted slag. Smelting chamber immersed into settling chamber to interphase boundary slag - matte. Settling chamber contains gas flue for withdrawal of sublimates and low blowing melting products.

EFFECT: increasing of noble metals extraction into matte.

8 cl, 3 dwg

FIELD: metallurgy.

SUBSTANCE: invention refers to hydrometallurgy, particularly to facility for extraction of precious metals, notably, gold and silver out of tails and other materials with high contents of fine fractions. The facility consists of a solution proof base and a border and also of a drainage system. The drainage system is made in form of a perforated tube with a gate at a discharge end. On the solution proof base there are successively laid: a layer of crushed stone of 2-5 mm size and of 150-200 mm thickness, then a layer of crushed stone of 5-40 mm size and 300-600 mm thickness, in the central part of which the perforated tube is located, then there is a layer of fabric out of geotextiles and a layer of crushed stone of 2-5 mm size and of 200-300 mm thickness; also the solution proof base is made with counter incline of 3-5° from each side from two counter borders into the direction of the perforated tube and also with the incline to horizon of 2-4° into the direction of the discharge end of the perforated tube in a vertical plane passing through the central longitudinal axis of the perforated tube.

EFFECT: facilitating extraction of precious metals out of materials with high contents of fine fractions and also simplification and reduction in cost of facility and its operation.

3 dwg

FIELD: metallurgy.

SUBSTANCE: invention concerns method of golden-antimonial-arsenical sulphide concentrates processing. Method includes melting of concentrates into slag and matte with gold concentration in matte and with condensation of formed arsenious sublimate and gold extraction from melted matte by antimony melt. At that before gold extraction into matte after separation of slag it is introduced soda at stoichiometric ratio to sulphide of antimony 3:1. Gold extraction is implemented by means of feeding matte melt in disperse state under antimony melt.

EFFECT: increasing of complex extraction level of valuable components from concentrate, in increasing of gold extraction speed, in reduction of materials consumption and equipment level of sophistication.

4 cl, 1 ex

FIELD: noble metal hydrometallurgy.

SUBSTANCE: invention relates to method for acid leaching of platinum method from secondary raw materials, in particular from ceramic support coated with platinum metal film. Target metals are leached with mixture of hydrochloric acid and alkali hypochlorite at mass ratio of OCl-/HCL = 0.22-0.25 and redox potential of 1350-1420 mV.

EFFECT: decreased leaching temperature, reduced cost, improved platinum metal yield.

2 ex

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