RU2293779C2 - Method of recovering and concentrating germanium from solutions - Google Patents

Abstract

FIELD: rare metal technology.

SUBSTANCE: method comprises precipitation of germanium in the form of scarcely dissoluble organic derivatives with mixture of hydroxycarboxylic acid and long-chain amine, the former, in particular, being tartaric, citric, or oxalic acid and the latter N-cetylpyridinium chloride or alkyldimethylbenzylammonium chloride at molar proportion of 2 to 6 per mole germanium. Method can be applied in processing of germanium-containing solutions and ammonia-tar liquors in by-product-coking industry.

EFFECT: increased degree of recovery and concentration of germanium, reduced consumption of reagents.

3 cl, 6 tbl, 5 ex

Description

The invention relates to the metallurgy of rare metals, in particular to methods for the extraction and concentration of germanium, and can be used in the processing of germanium-containing solutions and supra-tar waters of coke production.

Several hydrometallurgical methods are known - precipitation, sorption, extraction - extraction of germanium from complex chemical compositions of solutions obtained after leaching of rare-metal products of germanium-containing wastes, sublimates and tar waters.

A method for sorption of germanium using the epoxyamine anion exchange resin AN-31 [1], as well as an improved method for the production of germanium-selective ionite of this class [2] is known more than others. It should be noted several developed methods of desorption of germanium from anionite AN-31: solid-phase desorption with alkaline agents [3] and desorption in the form of germanium tetrachloride with hydrochloric acid at elevated temperatures [4]. However, all these technical solutions do not allow to eliminate the disadvantages inherent in the sorption method - low kinetic parameters and low selectivity of sorption of germanium, as well as difficulties in the regeneration of anion exchange resin and a low degree of concentration of germanium.

As a result of the information search, it was found that the closest analogue in terms of the set of essential features and purpose is the analogue [5, p. 353; 6, p. 181], in which there is a method for extracting and concentrating germanium from solutions, including precipitating it in the form of sparingly soluble organic compounds with tannin.

The implementation of this method involves mixing purified from suspended particles of a germanium-containing solution with an alkaline solution of oak extract, acidification with sulfuric acid to coagulate the precipitate, thickening and separating the tannin-germanium precipitate by filtration.

Despite a number of advantageous aspects, this method also has significant disadvantages due to the high consumption coefficients of the precipitant in the presence of impurities, the need for precipitation and coagulation from solutions of a certain acidity, as well as a low degree of concentration of germanium in organic sediment. This leads to the need for a long time to heat the reaction mass and to recycle the primary precipitate [7], which significantly complicates the process, increases its duration and the number of operations.

The present invention is aimed at eliminating the above disadvantages, namely increasing the degree of extraction and concentration of germanium, the intensification of the deposition and precipitation, reducing the consumption of reagents.

The technical result is achieved in that the deposition of germanium from solutions in the form of sparingly soluble organic compounds is carried out with a mixture of hydroxycarboxylic acid and a long chain amine; tartaric, citric or oxalic acids are used as hydroxycarboxylic acid, and N-cetylpyridinium chloride or alkyldimethylbenzylammonium chloride as a long chain amine in a molar ratio of from 2 to 6 each per mole of germanium.

The invention consists in the following.

The starting materials for processing can be neutral and acidic solutions with complex chemical composition containing trace amounts of germanium against the background of macro amounts of associated impurities obtained after leaching of germanium-containing raw materials, waste and sublimates of metallurgical processes or tar tar waters of coke production. A hydroxy carboxylic acid and a long chain amine are introduced into a germanium-containing solution in a specific ratio. As hydroxycarboxylic acid, tartaric, citric or oxalic acids are used, and the long chain amine is N-cetylpyridinium chloride (CPC) in a molar ratio of 2 to 6 each per mole of germanium. After the introduction of precipitating components, a sparingly soluble compound containing germanium is formed in the solution. The selectively formed sparingly soluble germanium product is separated from the liquid phase by known methods - filtration, centrifugation, or by blowing air through a solution, resulting in the formation of an anhydrous hydrophobic product during coagulation at a developed mobile liquid-gas interface. The product obtained by these methods is a germanium concentrate suitable for subsequent processing by known methods (electrolysis, cementation, distillation) into a marketable product - compounds or metal.

A comparative analysis of the known technical solutions and the claimed invention allows to conclude that the invention is not known from the prior art and meets the criterion of "novelty."

The inventive method of extraction and concentration of germanium meets all the criteria of patentability.

The invention proposed for patent protection has an inventive step, since its essence for a specialist in the metallurgy of rare and trace metals does not explicitly follow from the prior art, i.e. no solutions have been identified with signs that match the distinguishing features of the proposed method, and therefore, the fame of the distinctive features to the technical result indicated by the applicant cannot be confirmed.

The claimed invention is industrially applicable, as it can be used in production for its intended purpose, i.e. for the processing of germanium-containing solutions of metallurgical production and tar tar waters of coke production.

EXAMPLES OF PERFORMING THE METHOD

Example 1

Hydroxycarboxylic acids and a long chain amine in the ratio Ge: hydroxycarboxylic acid: CPC = 1: 1: 3 at room temperature and after 1 hour of filtration were introduced into a solution simulating suprasmol water with a germanium concentration of 0.0658 g / dm ³ and a pH of 2.8. the precipitate was separated and the degree of precipitation was determined by changing the concentration of germanium in the filtrate. The results are shown in table 1.

Table 1
Precipitation of germanium with hydroxycarboxylic acids and CPC The name of the complexing agent The residual content of Ge in the filtrate, g / DM ³ The degree of deposition of Ge,% lemon acid 20.1 68,2 oxalic acid 11.2 82.3 wine acid 1.3 97.9

Example 2

From a sulfate solution after leaching of sublimates of the composition, g / dm ³ : 0,031 Ge; 32.2 Zn; 6.5 As; 0.9 Fe; 1.8 Cu; 0.02 Sb; A pH of 1.4 was carried out by deposition of germanium with tartaric acid and CPC at a different ratio, and tannin (reactive purity) with different flow coefficients was used for comparison (Table 2). The chemical composition of the precipitate obtained by the deposition of germanium in the ratio Ge: tartaric acid: CPC = 1: 4: 2,%: 7.42 Ge; 1.8 Sb; 1.3 As; 0.01 Cu; 0.057 Fe; 0.014 Zn, and the composition of the precipitate upon precipitation with tannin in a weight ratio of tannin: Ge = 50: 1,%: 2.03 Ge; 1.3 Sb; 9.55 As; 0.16 Cu; 6.8 Fe, 1.7 Zn.

table 2
Germanium precipitation with tartaric acid-CPC and tannin Precipitation with tartaric acid-CPC Tannin precipitation The molar ratio of Ge: tartaric acid: CPC The weight ratio of precipitant / Ge, g / g The degree of deposition of Ge,% The weight ratio of tannin / Ge, g / g The degree of deposition of Ge,% 1: 2: 2 12.0 71.8 10 22.7 1: 4: 2 16,0 94.0 25 72.8 1: 4: 3 20,0 93.0 fifty 93.7

Example 3

From solutions of various compositions after sulfuric acid leaching of germanium-containing sublimates, the latter was precipitated with tartaric acid and CPC in a different ratio. After one hour of contact at room temperature, the precipitate formed was separated and the residual germanium content in the solution and its degree of precipitation were determined. The results are shown in tables 3-5.

Table 3
Germanium precipitation from solution, composition, g / dm ³ : 0.029 Ge; 12.23 As; 74.5 Zn, 8.4 Cu pH precipitation The molar ratio during the deposition of Ge: tartaric acid: CPC The residual content of Ge in the filtrate, g / DM ³ The degree of deposition of Ge,% 1.45 1: 2: 6 0.014 48.5 1: 4: 6 0.012 58.6 1: 6: 6 0.006 77.5 2.0 1: 2: 6 0.0128 52.9 1: 4: 6 0.0119 56.3 1: 6: 6 0.005 81.6 Table 4
Precipitation of germanium with tartaric acid and CPC from a solution, composition, g / dm ³ : 0.10 Ge; 50.0 Zn, 6.2 Cu; 11.4 H ₂ SO ₄ The molar ratio during the deposition of Ge: tartaric acid: CPC The residual content of Ge in the filtrate, g / DM ³ The degree of deposition of Ge,% 1: 1: 3 0,034 64,2 1: 2: 3 0.004 95.7 1: 3: 3 0.005 94.6 1: 2: 2 0.010 89.4 1: 2: 4 0.006 93.5 1: 2: 6 0.009 90.1 Table 5
Precipitation of germanium with tartaric acid and CPC from solution, composition, g / dm ³ : 0.587 Ge; 20.54 As; 58.6 Zn; Cu traces; 20.7 H ₂ SO ₄ The molar ratio during the deposition of Ge: tartaric acid: CPC The residual content of Ge in the filtrate, g / DM ³ The degree of deposition of Ge,% 1: 0.7: 1.4 0.422 25.7 1: 2.0: 1.4 0,082 85.3 1: 4.0: 1.4 0,060 88.9 1: 5.5: 1.4 0.130 75,4 1: 0.7: 2.7 0.270 51,4 1: 1.4: 2.7 0,039 92.9 1: 2.0: 2.7 0.005 99.1 1: 4.0: 2.7 <0.001 > 99.8 1: 5.5: 2.7 <0.001 > 99.8

Example 4

It differs from Example 3 in that alkyldimethylbenzylammonium chloride (ADBMAX) with a different hydrocarbon chain length was used as a long chain amine. The obtained results of the deposition of germanium are presented in table.6.

Table 6
The precipitation of germanium with tartaric acid and ADMBAH, taken in a molar ratio of 1: 2: 3, from solution, composition, g / dm ³ : 0,094 Ge; pH = 2.0 The length of the hydrocarbon radical ADMBAH The residual content of Ge in the filtrate, g / DM ³ The degree of deposition of Ge,% C ₁₀ -C ₁₆ 0,031 64.9 C ₁₂ -C ₁₄ 0,028 68.3 C ₁₆ -C ₁₈ 0,044 50,2

Example 5

From a germanium-containing solution of the composition, g / dm ³ : 0.96 Ge; 42.65 Zn, 1.1 Cu; As 26.4; 11.4 N ₂ SO ₄ after sulfuric acid leaching of electrostatic dust and their sublimates, composition,%: 0.42 Ge; 22.9 Zn; 0.51 Cu; As 22.3, germanium was precipitated with tartaric acid and alkyldimethylbenzylammonium chloride (KATAPAV) with a length of the hydrocarbon radical C ₁₂ -C ₁₄ at a molar ratio of germanium: tartaric acid: KATAPAV = 1: 2: 3 (weight ratio was 1: 4: 28) . The reagent solutions in the indicated amount were added with stirring to the precipitated germanium-containing solution: first, tartaric acid, and then the long-chain amine. After contact for 15 minutes, stirring was stopped to form a precipitate, and after 12 hours of settling of the resulting dispersion, the liquid phase was separated from the solid phase by filtration on a suction filter. As a result, the degree of deposition of germanium was 86.6%, and the percentage of the resulting precipitate was as follows: germanium - 1.94; copper - 0.86; zinc - 7.23; arsenic - 1.7; silicon oxide - 1.0; tin - 0.04; iron - 1.57; calcium oxide - 4.9; sulfur - 6.1.

The implementation of the proposed method for the extraction and concentration of germanium in comparison with the most well-known technical solutions, including those selected as a prototype, creates the following set of advantages:

- simplicity and effectiveness of deep deposition of germanium;

- expanding the acidity range of the processed solutions and eliminating the operation from pre-treatment (neutralization) before precipitation;

- improving the quality of the concentrate due to a more complete realization of the reactivity of the introduced precipitating components and the ability to achieve the optimal ratio Ge: hydroxycarboxylic acid: CPC;

- high selectivity of precipitation, since the concomitant ions of non-ferrous metals, as well as iron, antimony and arsenic are not prone to the formation of sparingly soluble compounds with hydroxycarboxylic acid and long-chain amine, as a result of which the consumption of reagents is reduced by eliminating their binding by impurity ions;

- intensification and simplification of the technology for the separation of germanium due to the ability of the sublate salt of germanium to flotation separation from the volume of the solution.

Literature

1. Sobinyakova N.M., Dunaevskaya V.V., Kraineva L.G. A.S. USSR No. 279952, BI, 1972, No. 19, p. 260. The method of extraction of germanium from solutions by sorption.

2. Chetverikov A.F., Grachev L.L., Samborsky I.V. A.S. USSR No. 288301, BI, 1970, No. 36, p. 122. A method of obtaining a germanium-selective ion exchanger.

3. Slobtsov L.E., Zastavny A.I., Nikolskaya L.L. and others A.S. USSR No. 393340, BI, 1973, No. 33, p. 102.

4. Slobtsov L.E., Nikolskaya L.L., Khilko M.E. and others A.S. USSR No. 793644, BI, 1981, No. 1, p. 38. Method for desorption of germanium from anion exchange resins.

5. Tananaev I.V., Shpirt M.Ya. Chemistry Germany. M .: Chemistry, 1967, 451 p.

6. Chemistry and technology of rare and trace elements. Under. ed. Bolshakova K.A., 1976, part 2, 360 p.

7. Avlasovich L.M., Poladyan V.E., Andrianov A.M. Improving the process of extracting germanium from tar waters. // Non-ferrous metals. 1990. No. 2. pg. 62-63.

Claims (3)

1. The method of extraction and concentration of germanium from solutions, including its precipitation in the form of sparingly soluble organic compounds, characterized in that the precipitation is a mixture of hydroxycarboxylic acid and a long chain amine. 2. The method according to claim 1, characterized in that tartaric, citric or oxalic acids are used as hydroxycarboxylic acid, and N-cetylpyridinium chloride or alkyldimethylbenzylammonium chloride as a long chain amine. 3. The method according to claim 1, characterized in that tartaric acid is used as the hydroxy carboxylic acid, and N-cetyl pyridinium chloride as a long chain amine in a molar ratio of from 2 to 6 each per mole of germanium.