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INVENTION
Patent of the Russian Federation RU2293779

METHOD OF EXTRACTION AND CONCENTRATION OF GERMANY FROM SOLUTIONS

The name of the inventor: Stanislav Stepanovich Naboychenko (RU); Swan Andrey Borisovich (RU); Maltsev Gennady Ivanovich (RU); Khrennikov Alexey Alexandrovich (RU); Radionov Boris Konstantinovich (RU); Shidlovskaya Irina Petrovna (RU); Dubrovin Pavel Viktorovich
The name of the patent owner: Limited Liability Company "Mednogorsk copper-smelting plant"
Address for correspondence: 462270, Orenburg Region, Mednogorsk, ul. Zavodskaja, 1, Open Company "Mednogorsk copper-copper combine"
Date of commencement of the patent: 2005.01.27

The invention relates to the metallurgy of rare metals, in particular to methods for extracting and concentrating germanium, and can be used in the processing of germanium-containing solutions and supraminate waters of coke-chemical production. The method for extracting and concentrating germanium from solutions involves the precipitation of germanium in the form of sparingly soluble organic compounds with a mixture of oxycarboxylic acid and a long chain amine. As the hydroxy acid, tartaric, lemonic or oxalic acids are used, and as a long chain amine, N-cetylpyridinium chloride (CTC) or alkyl dimethylbenzylammonium chloride in a molar ratio of 2 to 6 each per mole of germanium. The technical result is an increase in the degree of recovery and concentration of germanium, intensification of the process of precipitation and precipitation, a reduction in the consumption of reagents.

DESCRIPTION OF THE INVENTION

The invention relates to the metallurgy of rare metals, in particular to methods for extracting and concentrating germanium, and can be used in the processing of germanium-containing solutions and supraminate waters of coke-chemical production.

Several hydrometallurgical methods are known - precipitation, sorption, extraction - extraction of germanium from chemical-complex solutions obtained after leaching of rare-metal products of germanium-containing waste, sublimates and over-water.

The method of sorption of germanium with the help of epoxyamine anionite AN-31 [1] is known more than others, and an improved method of obtaining selective for germanium ionite of this class [2]. It should be noted several developed methods for desorption of germanium from anionite AN-31: solid-phase desorption by alkaline agents [3] and desorption in the form of germanium tetrachloride with hydrochloric acid at elevated temperature [4]. However, all these technical solutions do not allow to eliminate the drawbacks inherent in the sorption method-low kinetic indices and low selectivity of germanium sorption, and the difficulties of regenerating the anion exchanger and the low degree of concentration of germanium.

As a result of the information search conducted, it is established that the closest analogue in terms of the totality of essential characteristics 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 the germanium-containing solution that has been purified from suspended particles with an alkaline solution of oak extract, acidifying with sulfuric acid to coagulate the precipitate, thickening and separating the tannin-germanium precipitate by filtration.

Despite a number of winning moments, this method has significant drawbacks due to high consumption coefficients of the precipitator in the presence of foreign impurities, the need for deposition and coagulation from solutions of a certain acidity, and a low degree of concentration of germanium in the organic precipitate. This leads to the need for a long time to heat the reaction mass and recirculate the primary sediment [7], which significantly complicates the process, increases its duration and the number of operations.

The present invention is directed to eliminating the above disadvantages, namely, increasing the recovery and concentration of germanium, intensifying the precipitation and precipitation process, and reducing the consumption of reagents.

The technical result is achieved by the fact that the precipitation of germanium from solutions in the form of sparingly soluble organic compounds leads a mixture of oxycarboxylic acid and a long chain amine; As the hydroxycarboxylic acid, tartaric, citric or oxalic acids are used, and as a long chain amine, N-cetylpyridinium chloride or alkyl dimethylbenzylammonium chloride in a molar ratio of 2 to 6 each per mole of germanium.

The essence of the invention is as follows.

As raw materials for processing, neutral chemical and acidic solutions containing germanium microcounts against the background of macroquantities of accompanying impurities obtained after leaching of germanium-containing raw materials, waste and sublimates of metallurgical processes or supraminate waters of coke-chemical production can serve as raw materials for processing. A hydroxycarboxylic acid and a long chain amine are introduced into the germanium-containing solution in a certain ratio. As the hydroxycarboxylic acid, tartaric, citric or oxalic acids are used, and the long chain amine N-cetylpyridinium chloride (CPC) in a molar ratio of 2 to 6 each per mole of germanium. After the introduction of the precipitating components in the solution, a poorly soluble compound containing germanium is formed. The selectively formed low-solubility germanium product is separated from the liquid phase by known methods - filtration, centrifugation, or by blowing air through the solution, resulting in the formation of anhydrous hydrophobic product in the process of coagulation on the developed mobile fluid-gas interface. The product obtained by these methods is a germanium concentrate suitable for subsequent processing by known methods (electrolysis, carburizing, distillation) to a commodity product - compounds or metal.

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

The claimed method of extracting and concentrating germanium meets all criteria of patentability.

The invention proposed for patent protection has an inventive level, since its essence for a specialist dealing with the metallurgy of rare and dispersed metals does not explicitly follow from the prior art, i. E. No solutions have been identified that have characteristics that coincide with the distinguishing features of the claimed method, and hence the knownness of the distinctive features to the technical result indicated by the applicant can not be confirmed.

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

EXAMPLES OF THE FASHION EXECUTION

Example 1

Oxycarboxylic acids and long chain amine were introduced into a solution simulating supramolecular water with germanium concentration of 0.0658 g / dm ³ and pH 2.8 in the ratio Ge: oxycarboxylic acid: CTC = 1: 1: 3 at room temperature and after 1 hour of contact by filtration The precipitate was separated and the degree of its precipitation was determined from the change in the concentration of germanium in the filtrate. The results are shown in Table 1.

Example 2

From the sulphate solution after leaching of the 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; PH 1.4, germanium was precipitated with tartaric acid and CPC at different ratios, and for comparison, tannin (reactive purity) was used with different expenditure coefficients (Table 2). The chemical composition of the precipitate obtained by precipitation 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.

Example 3

From solutions of different composition 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 of the solution determined and the degree of its precipitation. The results are shown in Tables 3-5.

Example 4

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

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 the sulfuric acid leaching of electrofilter dusts and their sublimates, composition,%: 0.42 Ge; 22.9 Zn; 0.51 Cu; As, the precipitation of germanium with tartaric acid and alkyl dimethylbenzylammonium chloride (CATAPAV) with the length of the C ₁₂ -C ₁₄ hydrocarbon radical was carried out at a molar ratio of germanium: tartaric acid: CATAPAB = 1: 2: 3 (the weight ratio was 1: 4: 28) . Reagent solutions in this amount were added with stirring to the precipitated germanium-containing solution: firstly tartaric acid and then a long-chain amine. After contact, stirring was stopped for 15 minutes to form a precipitate, and after 12 hours of settling the resulting dispersion, the liquid phase was separated from the solid by filtration on the nutch filter. As a result, the degree of precipitation of germanium was 86.6%, and the percentage composition of the obtained 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 of extraction and concentration of germanium in comparison with the most well-known technical solutions, including those chosen as a prototype, creates the following set of advantages:

- simplicity and efficiency of deep deposition of germanium;

- expansion of the acidity range of the processed solutions and elimination of the operation from pre-treatment (neutralization) before sedimentation;

- Improvement of the quality of the concentrate due to a more complete realization of the reactivity of the injected precipitating components and the possibility of achieving the optimum ratio of Ge: oxycarboxylic acid: CPC;

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

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

USED ​​BOOKS

1. Sobinyakova NM, Dunaevskaya VV, Kraineva LG A.S. USSR № 279952, BI, 1972, №19, p.260. Method of extracting germanium from solutions by sorption.

2. Chetverikov AF, Grachev LL, Samborskiy IV A.S. USSR № 288301, БИ, 1970, №36, стр.122. Method of obtaining selective for germanium ion exchanger.

3. Slobtsov L.E., Zastavny AI, Nikolskaya L.L. And others. USSR No. 393340, BI, 1973, No. 33, p.102.

4. Slobtsov LE, Nikolskaya LL, Hilko ME And others. USSR № 793644, БИ, 1981, №1, стр.38. The method of desorption of germanium from anion-exchange resins.

5. Tananaev IV, Shpirt M.Ya. Chemistry of germanium. Moscow: Chemistry, 1967, 451 p.

6. Chemistry and technology of rare and scattered elements. Under. Ed. Bolshakova KA, 1976, part 2, 360 with.

7. Avlasovich LM, Poladyan VE, Andrianov AM Improvement of the process of germanium recovery from supramine waters. // Non-ferrous metals. 1990. № 2. Pp.62-63.

CLAIM

A method for extracting and concentrating germanium from solutions, comprising precipitating it in the form of sparingly soluble organic compounds, characterized in that the precipitation is carried out with a mixture of an oxycarboxylic acid and a long chain amine.

2. A process according to claim 1, characterized in that tin, lemon or oxalic acid is used as the hydroxycarboxylic acid, and N-cetylpyridinium chloride or alkyl dimethylbenzylammonium chloride is used as the long chain amine.

3. The process of claim 1, wherein tinic acid is used as the hydroxycarboxylic acid, and N-cetylpyridinium chloride is used as a long chain amine in a molar ratio of 2 to 6 each per mole of germanium.

print version
Date of publication 14.03.2007gg

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