Method for separating indium and gallium from acid sulfate solution

FIELD: inorganic chemistry, chemical technology.

SUBSTANCE: invention relates to technology for producing rare and scattered elements. Invention proposes using a mixture of isododecylphosphetanic and dialkylphosphinic acid in organic solvent as an extractant. Invention provides enhancing selectivity of extraction by metal-impurities and separation of indium from gallium, and possibility for carrying out re-extraction of metals from organic phase with sulfuric acid solutions in the concentration 200-350 g/dm3. Invention can be used in extraction and separation of gallium and indium from acid sulfate solution of the complex composition.

EFFECT: improved separating method.

4 tbl, 4 ex

 

The invention relates to the field of technology of rare and scattered elements, and analytical chemistry and can be used for the separation and concentration of indium and gallium from acidic sulfate solutions, complex in their chemical composition. Such solutions are obtained hydrometallurgical processing of concentrates and intermediates lead-zinc production, as well as their analytical dissection. To extract indium from technological solutions of zinc production is a method using extraction, to allow India concentration and separation from most of the impurities. However, the selectivity of the used process for iron and Gaul low, which leads to the need for additional technological operations, allowing to obtain high purity indium. While gallium, available technological solutions, is removed and, as a rule, irreversibly lost.

The known method of separation of indium and gallium from solutions of acid leaching Waelz zinc oxide production, based on differences in the pH of the allocation of the hydroxides of indium and gallium [Say, Vigin, Pietoro, Amernic. Rare and trace elements. Chemistry and technology. VOL. - M.: "MISIS", 2003, pp.118-125]. The disadvantage of this method is the need megatr the private transactions precipitation-dissolution, which leads to large losses of indium and gallium. In addition, the result is a concentrate of India are of low quality, requiring further processing, and gallium is concentrated in alkaline solutions containing large amounts of impurities (Zn, Al, and others).

The method for extracting indium from acidic sulfate solutions using as extractant dialkylphosphorous acid (dapc) [patent of Russia №2186141 from 28.03.2001 g]. Using this method allows reextraction India with aqueous solutions of 250-450 g/DM3of sulfuric acid. The disadvantage of this method is the low degree of separation of indium and gallium in the case of extraction from solutions containing both metals.

There is also known a method of extracting indium from acidic sulfate solutions with a mixture of di-2-ethylhexylamine acid (D2EGFK) and izodolasytonecyl acid (IDFC) [patent of Russia №2238994 on 17.02.2003 g], which allows reextraction India solutions 250-450 g/DM3of sulfuric acid. The disadvantage of this method is the low degree of separation of indium and gallium in their joint presence in the source water solution.

As a result, in accordance with paragraph 7 of article 21 of the Law of information retrieval in accordance p Rules, it was found that the closest analog is the set of essential characteristics and purpose is similar, proposed by the applicant (M.S.Zee, J.G.Ahn, E.G.Zee, Hydrometallurgy, 2002, 63, R-276), which opened the way for the separation of indium and gallium from acidic sulfate solutions, including extraction with an extractant containing organophosphorus reagent D2EGFK in an organic solvent, and the re-extraction solution of hydrochloric acid. A significant disadvantage of this method is the low selectivity of the extraction process on such metal impurities, such as zinc, iron, copper, arsenic, antimony, cadmium, etc. in Addition to Stripping of indium and gallium must be used hydrochloric acid solutions. This leads to contamination of the technological solutions of Zn-production and complication of their further processing.

The technical result of the present invention is to increase the degree of separation of indium and gallium, increasing the selectivity of the extraction process of indium and gallium metal-impurities and simplification of the process due to the use for Stripping indium and gallium solutions of sulfuric acid.

This technical result is achieved by the method of separation of indium and gallium from acidic sulfate solutions, including extraction of metals with a solution of organophosphorus reagent in an organic diluent, is used as an extractant mixture izodolasytonecyl and dialkylphosphorous acids the ri ratio (vol.%): isotopeselective acid (IDFC) 10-20; dialkylphosphinate acid (dafc) 20-10; organic diluent else.

The extraction India conducted from the aqueous phase having a pH of 10-30 g/DM3for sulfuric acid, and reextraction India from the organic phase solution of sulfuric acid with a concentration of 200-350 g/DM3. The essence of the proposed method is illustrated by the following examples.

Example 1

Extracted indium and gallium from acidic sulfate solutions, staff (g/DM3): indium 1,1; gallium 0,49; sulfuric acid 15,7. As the organic phase used a solution in kerosene mixture IDFC and DFC, and the mixture D2EGFK with IDFC and DFK. In addition, as the extractant solution was used D2EGFK in kerosene (prototype). In table. 1 shows data on the distribution, extraction and separation of metals extraction. From the above table. 1 data shows that when using as a solvent a mixture containing 10-20% IDFC and 20-10% DFC; the rest of the kerosene, the values of distribution coefficients and degrees of extraction and partition coefficients of indium and gallium is much higher than for solutions in kerosene D2EGFK (prototype) or a mixture D2EGFK with IDFC and DFK.

Table 1
The distribution of indium and gallium between the phases of extraction depending on with whom tava extractant
The composition of the mixture, about. %Distribution and retrieval of elementsFactor separation βIn/Ga
IDFCDAPDInEInDGaEGa
03011,992,20,1613,874,4
525a 12.7of 92.70,1714,574,7
102023,993,00,119,9217
151523,595,90,109,1235
201024,896,10,1210,7207
25512,192,40,1613,875,6
30012,8of 92.70,1513,085,0
20-D2EGFK, 10-IDFCthe 17.394,50,2721,364,0
20-D2EGFK, 10-D is FC 16,894,40,2419,470
30-D2EGFK (prototype)18,995,00,3023,163,0

Example 2

Extracted indium from acidic sulphate solutions of different organic extractants containing kerosene mixture of organophosphorus acids in the ratio of 10 and 20 vol.% IDFC and 20 and 10 vol.% Dafc respectively (the proposed method), and 30 vol.% D2EGFK with 10% vol. IDFK. The extraction is carried out at a volume ratio between organic and aqueous phases O:b=1:2 and a temperature of 22°C. the Composition of the aqueous phase (g/DM3): indium 0,81; gallium 0,28; zinc 79,3; copper 1,12; cadmium 0,95; arsenic 1,12; antimony 0,22; iron (II) 4,3; iron (III) 0,19; sulfuric acid and 15.2. In table. 2 shows data on the distribution of metals extraction.

From the above table. 2 data suggest that when using as a solvent a mixture of organophosphorus acids IDFC and dafc selectivity of the extraction process India is higher as in Gaul, and other metal impurities in comparison with the extractant D2EGFK.

Table 2
The distribution coefficients of the components during extraction, India
The extractant, about. % The distribution coefficients
InZnFe(II)Fe(III)CdCuAsSb
The proposed method is:
1) 20-IDFC

10-dafc
24,70,010,00710,60,020,0030,0020,2
2) 10-IDFC

20-dafc
23,70,010,0079,90,020,0030,0020,2
20-D2EGFK

10-IDFC
the 17.30,020,0138,20,050,030,020,4
Prototype

30-D2EGFK
18,70,030,0840,40,050,030,020,4

The aqueous phase after extraction extraction India is neutralized, for example, soda to a pH of 2.4 and is directed to the extraction of gallium from the same extractants. Extraction was carried out with a ratio A:B==1:3, and the temperature 21,8°C. are Given in table. 3 the data show that sat is aktivnosti process of extraction of gallium compounds IDFC and dafc higher compared to D2EGFK and its mixture with IDFC.

Table 3
The distribution coefficients of related impurities in the extraction of gallium
The extractant, vol.%The distribution coefficients
GaZnFe(II)Fe (III)CdCuAsSb
The proposed method is:
1) 20-IDFC

10-dafc
20,13,20,0236,10,050,030,010,3
2) 10-IDFC

20-dafc
19,22,90,0235,20,050,030,010,3
20-D2EGFK

10-IDFC
19,87,10,0343,50,070,040,030,5
Prototype

30-D2EGFK
20,515,30,0448,70,080,050,030,6

<> Example 3

From the organic phase containing a mixture of 15% vol. IDFC and 15 vol.% Dafc in kerosene and 30% vol. D2EGFK in kerosene (prototype), are reextraction indium and gallium with sulphuric acid solutions of different concentrations. The indium content in the organic phase 0,93 g/DM3and gallium 0.32 g/DM3. The ratio of A:b is 10:1, the temperature of 21.6°C. In the table. 4 shows data on the effect of the concentration of sulfuric acid in reextracted aqueous solution on the extraction of indium and gallium from extracts.

tr>
Table 4
The dependence of the extraction of indium and gallium in the Stripping of the concentration of sulfuric acid in the aqueous phase
The concentration of sulfuric acid g/DM3Extraction into the aqueous phase by Stripping, %
20% vol. IDFC + 10% vol. Dafc in kerosene30 D2EGFK% vol. in kerosene (prototype)
IndiesgalliumIndiesgallium
15029,630,78,5the 9.7
20073,475,111,812,6
250to 78.381,016,517,4
30083,686,220,722,1
35088,589,823,424,7
400and 88.8to 91.624,625,8
450of 89.191,929,330,2
50089,792,330,732,4

From the above table. 4 data shows that the effective reextracted indium and gallium from the organic phase in the case of using the mixture of organophosphorus acids IDFC and dafc can be carried out with solutions of sulfuric acid with a concentration of 200-350 g/DM3. When lower concentrations of sulfuric acid reextracted indium and gallium is rapidly deteriorating. The increase in the concentration of sulfuric acid of more than 350 g/DM3does not increase extraction in the aqueous phase metals, at the same time it increases the consumption of sulfuric acid. In the case of D2EGFK (prototype) reextracted indium and gallium in these conditions is much worse.

Example 4

Carry out the extraction process for the separation of indium and gallium from acidic sulfate solutions. As organic phase, use a solution in kerosene mixture of 20 vol.% IDFC and 10 vol.% DFK or solution in kerosene 30% vol. D2EGFK (protot the p). The aqueous phase served sulfate solution containing (g/DM3): indium 0,67; gallium 0,28; zinc 1,4; copper 0,21; iron (II) 3,1; iron (III) 0.2 and sulfuric acid 16,3. The extraction is carried out in counter-current mode in 3 stages when the volume ratio between organic and aqueous phases O:=1:3. The temperature of 20.7°C, the duration of mixing of the phases at each stage of 3 min Extraction India in the organic phase under these conditions is 99.6%, the separation factor of indium and gallium βIn/Ga=212. In the case of the extractant D2EGFK (prototype) removing India is 98.9 per cent, and the separation factor βIn/Ga 59.

The extract obtained was treated with an aqueous solution containing 250 g/DM3sulfuric acid in countercurrent mode 3 speed transmission with a ratio A:B=15:1 and mixing time on each stage 5 min. Concentration in aqueous solution after Stripping (g/DM3): indium 29,6; gallium 0,03; iron 7,6; zinc; 0,03; copper of 0.05. The total extraction of indium in the reextract is to 98.6%. When using as extractant D2EGFK (prototype) in these conditions, the total extraction India does not exceed 16.9 per cent. From the extract D2EGFK indium can be quantitatively extract only solution of hydrochloric acid. Of the used extract solution containing 400 g/DM3hydrochloric acid, extragere 97,6% India. The total number of stages of extraction and reqstr the work at the division of indium and gallium is 6.

The aqueous solution after extraction extraction India (raffinate) is neutralized with soda ash to a pH of 2.5 and sent for extraction of gallium same extractants. The number of stages of counter-current extraction of gallium 3, the ratio A:B=1:3, the extraction time at each step for 3 min Extraction of gallium in these conditions, using the mixture of reagents IDFC and DFK is 98,7%, and for D2EGFK 97,9%.

For the process of Stripping used a solution of 250 g/DM3sulfuric acid, the number of stages of the counter 3, the ratio A:B=30:1. The content of gallium in reextract 24.6 g/DM3total extraction of gallium were $ 97.6%, and the number of steps of the processes of extraction and re-extraction 6. In terms of counter-current total extraction of gallium was 96.2.

Thus, the use of the proposed method of separation of indium and gallium can increase the degree of separation of indium and gallium, to increase the selectivity of the process for metal impurities, to simplify the process through the use of for Stripping solutions of sulfuric acid, which allows to obtain aqueous solutions-reextractors, not containing chloride ions and convenient for further processing. In addition, this method provides the possibility of applying the proposed extractant for separation of gallium from aqueous solutions.

The method of separation of India and ha is Leah from acidic sulfate solutions, including extraction with an extractant containing organophosphorus reagent in an organic solvent, and reextraction, characterized in that as organophosphorus reagent, a mixture of izodolasytonecyl and dialkylphosphorous acids, with a ratio,%:

Isotopeselective acid10-20
Dialkylphosphinate acid10-20
Organic solventRest

the extraction is carried out at pH sulfate solutions 10-30 g/DM3and reextraction lead sulfuric acid solution with a concentration of 200-350 g/DM3.



 

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