ZA200801806B - Method of treating of zinc- and germanium containing solid-phase polymetallic mineral material - Google Patents
Method of treating of zinc- and germanium containing solid-phase polymetallic mineral material Download PDFInfo
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- ZA200801806B ZA200801806B ZA200801806A ZA200801806A ZA200801806B ZA 200801806 B ZA200801806 B ZA 200801806B ZA 200801806 A ZA200801806 A ZA 200801806A ZA 200801806 A ZA200801806 A ZA 200801806A ZA 200801806 B ZA200801806 B ZA 200801806B
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- South Africa
- Prior art keywords
- germanium
- zinc
- phase
- eluate
- solution
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 47
- 239000007790 solid phase Substances 0.000 title claims description 25
- 239000000463 material Substances 0.000 title claims description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims description 8
- 239000011707 mineral Substances 0.000 title claims description 8
- MRZMQYCKIIJOSW-UHFFFAOYSA-N germanium zinc Chemical compound [Zn].[Ge] MRZMQYCKIIJOSW-UHFFFAOYSA-N 0.000 title claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 63
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 63
- 239000007791 liquid phase Substances 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 29
- 229910052725 zinc Inorganic materials 0.000 claims description 29
- 239000011701 zinc Substances 0.000 claims description 29
- 238000002386 leaching Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003456 ion exchange resin Substances 0.000 claims description 16
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002955 isolation Methods 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 13
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 229940119177 germanium dioxide Drugs 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 238000005262 decarbonization Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000008186 active pharmaceutical agent Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 24
- 238000000605 extraction Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002893 slag Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000009856 non-ferrous metallurgy Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
The invention relates to non-ferrous metallurgy, in particular to methods of hydrometallurgic processing of zinc- and germanium-containing solid-phase polymetallic mineral materials used for extracting germanium and zinc from said materials.
A relevant task of today is the development of technological processes of extraction of such valuable technology-related materials as germanium and zinc from base ores and also from after-products of pyrometallurgic fabrication of non-ferrous metals (slag, dust and other waste products of pyrometallurgic industry).
The fact that the abovementioned raw products represent sparingly soluble solid-phase materials that contain germanium and zinc in the form of a wide range of chemical compounds and also contain a great number of other accompanying chemical elements and compounds makes it necessary to develop special-purpose multi-stage methods of selective extraction of zinc and germanium, mainly to increase the ratio of their extraction.
A known method of processing of copper-smelting industry slag for obtaining germanium and zinc thereof [A.N. Zelikman, B.G. Korshunov.
Metallurgy of rare metals. M.: 1991, p. 258] comprises blowing coal dust with air through molten slag (the fuming process), wherein germanium and zinc are extracted in the form of oxides and collected in sublimates.
This method is characterized by a relatively high extent of extraction of the target components, but it consumes a lot of energy.
Methods that result more efficient in terms of energy saving are the methods of hydrometallurgic processing of the abovementioned raw materials for obtaining the target products, in particular, germanium and zinc, wherein the target component is dissolved as a result of leaching performed by a reagent of selective action, which ignores other components of the raw material when possible.
Such is the method of processing of copper-smelting industry dust for extracting germanium and zinc from said material [Proceedings of higher education institutes. Non-ferrous metallurgy, No. 3, 2006, p. 43], which was
— . chosen by the authors as the closest prototype.
According to this method the raw material is leached by a solution of sulfuric acid with concentration of 0.2 gram-molecule/dm?® at the ratio between liquid and solid phases of 1:3, whereupon the obtained pulp is used for selective extraction of germanium and zinc.
This method provides extraction of 65 — 85% of germanium and 75 — 85% of zinc, but these numbers are not sufficient.
It is an object of the present invention to provide a method for processing solid-phase polymetallic mineral material that provides extraction of germanium and zinc with increased extraction ratio.
According to the inventive method of processing of zinc- and germanium- containing solid-phase polymetallic mineral material, which comprises leaching of the material by means of water solution of a chemical reagent and subsequent treatment of the obtained pulp for extracting germanium and zinc, the leaching is performed with mechanical, abrasive and disintegrating influence, wherein the solution of a chemical reagent is embodied in the form of a : solution containing oxidant in the amount from 1.8 to 2.5 kg per 1 kg of germanium present in the source material, and hydroxide of an alkali metal in the amount that provides pH of the medium from 12 to 14, with the ratio between liquid and solid phases of 1:(3 - 8), then sorption sedimentation of germanium from the obtained pulp is done by passing it through ion-exchange resin, wherein the pulp has alkali added thereto in the amount that provides : pH of the medium from 13.5 to 14 and water in the amount that provides ratio between liquid and solid phases of 1:(5 - 8); the product obtained after sorption sedimentation of germanium is treated in an autoclave at a temperature of 120-250°C and pressure of 6-40 atm with subsequent isolation of the liquid phase, which is used for extracting zinc thereof, while germanium is eluated from the ion-exchange resin, and then the obtained eluate is used for extracting germanium thereof.
In a particular embodiment of the invention zinc is extracted in the form of zinc oxide by means of carbonization of liquid phase and isolation of precipitated sediment, its decarbonization and drying.
In a particular embodiment of the invention germanium is eluated by an alkali solution with concentration from 5 to 30 % of weight, whereupon germanium is extracted from the eluate in the form of germanium dioxide by means of acidation of the eluate to pH of 6.5-7.5, isolation of the precipitated sediment and its drying.
In a particular embodiment of the invention germanium is eluated by means of 1.1n — 5.0n solution of hydrochloric acid, whereupon germanium is extracted from the obtained eluate in the form of germanium dioxide by heating said eluate to a temperature not more than 90°C, isolation of the gas phase, its washing in the hydrolysis tower and drying of the precipitated sediment.
Experimental investigations conducted by the authors of the invention allowed developing a multi-stage procedure of processing various types of polymetallic mineral materials that provides extraction of germanium and zinc from said materials with increased extraction ratio.
According to the inventive method the process of leaching the raw material by a chemical reagent is performed under conditions that provide disintegrating and abrasive influence upon the treated material, resulting in development and activation of surface of its particles, as well as rapid renewal of the surface of contact between the liquid and solid phases, which stimulates the intensification of : the chemical reactions that take place during the leaching.
The solution chosen by the authors as the chemical reagent used for the leaching, which contains oxidant in the amount from 1.8 to 2.5 kg per 1 kg of germanium present in the raw material and hydroxide of an alkali metal in the amount that provides pH of the medium from 12 to 14, together with the chosen ratio between liquid and solid phases of 1:(3 - 8) used for performing the leaching, result in chemical processes that at this stage provide an extremely high extent of germanium extraction in the form of water-soluble germanium compounds, which are formed during the leaching process and are transferred to liquid phase during this stage.
The chosen conditions for the leaching process also provide extraction of substantial part of zinc in the form of its water-soluble compounds from the raw material.
The results of analyses showed that the process of leaching of the raw material with all abovementioned conditions observed provides selective extraction into liquid phase of up to (97 - 99) % of germanium and up to 60% of zinc, as early as during this stage of the process.
Disintegrating and abrasive influence upon the treated material during its leaching can be ensured, in particular, by conducting this process within a planetary mill. I
The oxidant that forms part of the chemical reagent can be embodied, in particular, in the form of sodium hypochlorite, hydrogen peroxide.
The technique of sorption sedimentation of germanium from the pulp obtained during the leaching process by passing it through ion- exchange resin allows selectively isolating germanium compounds from other components of the pulp. Here the conditions for conducting the process of sorption sedimentation of germanium, namely the pH value of the medium from 13.5 to 14 and the ratio between solid and liquid phases of 1.(5 - 8), were chosen by the authors experimentally and are optimal in terms of providing completeness of sorption of germanium on the surface of the ion- exchange resin. Specified values of the pH of the medium and the ratio between solid and liquid phases can be obtained by adding to the pulp necessary amounts of, respectively, hydroxide of an alkali metal and water.
Various ion-exchange resins capable of selectively sorbing germanium can be used for sorption sedimentation of germanium, in particular, ion-exchange resins of weakly basic type with secondary or tertiary amine active functional groups, macroporous polystyrene chelate weakly basic anionites, etc.
While treated inside an autoclave the product obtained after sorption sedimentation of germanium and being a mixture of liquid phase and solid particles undissolved during the leaching, which passed through ion-exchange resin the process of hydrothermal isolation of zinc, remaining in the solid phase, into liquid phase takes place. The modes of autoclave treatment of the specified product, namely the temperature of 120-250°C and pressure of 6-40 atm, were chosen by the authors experimentally and are optimal in terms of providing completeness and selectivity of isolation of zinc into liquid phase.
Separation of specified liquid phase from solid-phase products, for example by means of filtration, allows obtaining a liquid-phase product containing
: LJ zinc that was extracted during previous stages of the process, whereupon zinc can subsequently be extracted from said product by means of various known methods.
Extraction of germanium from ion-exchange resin is done by washing it from the surface of the ion-exchange resin by means of a solution of chemical substance, which provides desorption of germanium, with subsequent extraction of germanium from the obtained eluate by means of various known methods.
According to the inventive method, the target product in the process of zinc extraction can be the zinc oxide, which is obtained by means of carbonization of the liquid phase isolated after the autoclave treatment of the product, isolation of the precipitated sediment, decarbonization of the precipitated product and its drying. ~ According to the inventive method, the target product in the process of germanium extraction can be the germanium dioxide, which is obtained by desorption of germanium from the surface of the ion-exchange resin by means of an alkali solution with concentration from 5 to 30 % of weight, followed by acidation of the obtained eluate until obtaining pH value of 6.5-7.5, isolation of the precipitated sediment and its drying.
Germanium dioxide as the target product can also be obtained by desorption of germanium from the surface of the ion-exchange resin by means of a 1.1n — 5.0n solution of hydrochloric acid, heating of the obtained eluate to a temperature not more than 90°C, isolation of the gas phase, washing of the obtained gas-phase product in a pump and drying of the precipitated sediment.
The method is realized in the following way.
The raw zinc- and germanium-containing solid-phase polymetallic mineral material is subjected to leaching under conditions that provide mechanical abrasive and disintegrating influence upon the material. The process is performed, in particular, inside a planetary mill, where lump or grinded raw material is introduced together with a water solution, which comprises oxidant in the amount from 1.8 to 2.5 kg per 1 kg of germanium present in the material and hydroxide of an alkali metal in the amount that provides the pH of the medium from 12 to 14. Inside the mill the material is subjected to high dynamic loads (more than 20 G), whereupon the reaction mass becomes heated to 70-95 °C, together with grinding, breakage and abrasion of the treated material, whereupon the material becomes finely dispersed (degree of dispersion in the order of 10-40 : pm). The leaching process is conducted at the ratio between solid and liquid phases of 1:(3 - 8), which can be obtained by having calculated amount of water in the solution. Time of conducting the leaching process may vary from 5 min to 4 hours.
The pulp obtained during the leaching stage is passed through ion- exchange resin in order to obtain sorption sedimentation of germanium, for example, through a holder with ion-exchange resin installed in the reactor. The : process is conducted after adding to the pulp alkali in the amount that provides pH of the medium of 13.5 - 14 and water in the amount that provides ratio between solid and liquid phases of 1:(5 - 8). Here the pulp is passed through the holder in the countercurrent mode with respect to the flow of the alkali water solution. : The product obtained after sorption sedimentation of germanium is supplied to the autoclave, where its hydrothermal treatment takes place, at a temperature of 120-250°C and pressure of 6-40 atm, with duration between 40 min and 4 hours.
Then the liquid phase is isolated from the product obtained after the autoclave treatment, for example, by means of vacuum filtration. The obtained liquid phase is used for extracting zinc thereof.
Germanium is eluated from ion-exchange resin, and the obtained eluate is used for extracting germanium thereof.
Possibility of realization of the method is shown in the examples of specific embodiment.
Example 1.
Dump polymetallic slag from lead industry was used as raw material, said slag containing 5 % of weight of zinc and 0.04 % of weight of germanium, according to the data of mass-spectrum analysis.
The source slag was supplied to the planetary mill in the amount of 100 kg, also water solution containing 10 g/l of sodium hypochlorite was supplied in the amount calculated from the ratio of 2 kg of sodium hypochlorite per 1 kg of germanium contained in the slag. Also sodium hydroxide was supplied to the planetary mill, in the amount that provided the pH value of the medium of 13.5. Ratio of solid and liquid phases in the reaction medium equaled 1:4. The leaching process lasted about 50 min.
Pulp obtained during the leaching stage was supplied to the reactor by passing it through the holder with macroporous polystyrene weakly basic anionite of D403 model installed in the reactor, wherein the pulp had sodium hydroxide added thereto in the amount that provided the pH of the medium of 14 and water in the amount that provided ratio between solid and liquid phases of 1:6. The pulp was passed through the holder in the countercurrent mode with respect to the flow of the alkali water solution.
The product obtained after sorption sedimentation of germanium was supplied to the autoclave, where it was subjected to hydrothermal treatment at a temperature of 220°C and pressure of 30 atm during 2 hours. Liquid phase was isolated from the product obtained after the autoclave treatment by means of vacuum filtration.
The filtered liquid-phase product was supplied to a two-step carbonization tower operating in the foam mode. Carbon dioxide was used as a carbonizing agent. After carbonization Zn(OH)2 COs was obtained, which was then subjected to decarbonization by heating it to 300°C, thus obtaining zinc oxide as the final product. Output of zinc as compared to its content in the source slag amounted to 99.97%.
In order to extract germanium precipitated on the anionite, the holder with anionite was soaked in 20% solution of sodium hydroxide and then washed with water. The obtained eluate was acidated to pH of 7, wherein dihydrate germanium dioxide precipitated as sediment. The obtained sediment was filtered, dried and ignited at t=300°C.
Dioxide germanium was obtained as the final product. Output of germanium as compared to its content in the source slag amounted to 99.95%.
Example 2. :
The same raw material as in Example 1 was used. :
The source slag was supplied to the planetary mill, as well as water solution containing 30% solution of hydrogen peroxide, in the amount calculated from the ratio of 2.4 kg of hydrogen peroxide per 1 kg of germanium contained in the slag. Also sodium hydroxide was supplied to the planetary mill, in the amount that provided the pH of the medium of 13.8.
Ratio of solid and liquid phases in the reaction medium equaled 1:5. The leaching process lasted 30 min.
Pulp obtained during the leaching stage was supplied to the reactor by passing it through the holder with macroporous polystyrene weakly basic anionite of D403 model installed in the reactor, wherein the pulp had sodium hydroxide added thereto in the amount that provided the pH of the medium of 14 and water in the amount that provided ratio between solid and liquid phases of 1:6. The pulp was passed through the holder in the countercurrent mode with respect to the flow of the alkali water solution.
The product obtained after sorption sedimentation of germanium was supplied to the autoclave, where it was subjected to hydrothermal treatment at a temperature of 220°C and pressure of 30 atm during 2 hours. Liquid phase was isolated from the product obtained after the autoclave treatment by means of vacuum filtration.
The filtered liquid-phase product was supplied to a two-step carbonization tower operating in the foam mode. Carbon dioxide was used as a carbonizing agent. After carbonization Zn(OH)2 COs was obtained, which was then subjected to decarbonization by heating it to 300°C, thus obtaining zinc oxide as the final product. Output of zinc as compared to its content in the source slag amounted to 99.90%.
In order to extract germanium precipitated on the anionite, the holder with anionite was soaked in 1.5n solution of hydrochloric acid and then washed with water. The obtained eluate was heated to a temperature of 85 - 90°C, and as a result the obtained germanium tetrachloride emerged in the form of gas, which was directed to the tower for conducting the process of hydrolysis with subsequent isolation of the precipitated sediment and its drying.
Dioxide germanium was obtained as the final product. Output of germanium as compared to its content in the source slag amounted to 99.97%.
Claims (4)
1. Method of processing of zinc- and germanium-containing solid-phase polymetallic mineral material, which comprises leaching of the material by means of water solution of a chemical reagent and subsequent treatment of the obtained pulp for extracting germanium and zinc, characterized in that the leaching is performed with mechanical, abrasive and disintegrating influence, wherein the solution of a chemical reagent is embodied in the form of a solution containing oxidant in the amount from 1.8 to 2.5 kg per 1 kg of germanium present in the source material, and hydroxide of an alkali metal in the amount that provides pH of the medium from 12 to 14, with the ratio between liquid and solid phases of 1:(3 - 8), then sorption sedimentation of germanium from the obtained pulp is done by passing it through ion-exchange resin, wherein the pulp has alkali added thereto in the amount that provides pH of the medium from 13.5 to 14 and water in the amount that provides ratio between liquid and solid phases of 1:(5 - 8); the product obtained after sorption sedimentation of germanium is treated in an autoclave at a temperature of 120-250°C and pressure of 6-40 atm with subsequent isolation of the liquid phase, which is used for extracting zinc thereof, while germanium is eluated from the ion-exchange resin, and then the obtained eluate is used for extracting germanium thereof.
2. A method as claimed in Claim 1, characterized in that zinc is extracted in the form of zinc oxide by means of carbonization of liquid phase and isolation of precipitated sediment, its decarbonization and drying.
3. A method as claimed in Claim 1, characterized in that germanium is eluated by an alkali solution with concentration from 5 to 30 % of weight, whereupon germanium is extracted from the eluate in the form of germanium dioxide by means of acidation of the eluate to pH of 6.5-7.5, isolation of the precipitated sediment and its drying.
4. A method as claimed in Claim 1, characterized in that germanium is ra eluated by means of 1.1n — 5.0n solution of hydrochloric acid, whereupon germanium is extracted from the obtained eluate in the form of germanium dioxide by heating said eluate to a temperature not more than 90°C, isolation of the gas phase, its washing in the hydrolysis tower and drying of the precipitated sediment.
DS. Method of processing of zinc- and germanium-containing solid-phase +, polymetallic mineral material substantially as described herein with reference to the examples. : : Dated this 29nd day of February 2008 % a oo Brian Bacon & Associates Inc. Applicant's Patent Attorneys N
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2007108704/02A RU2337164C1 (en) | 2007-03-06 | 2007-03-06 | Method of processing zinc and germanium containing solid phase polymetallic mineral material |
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| ZA200801806B true ZA200801806B (en) | 2009-10-28 |
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| ZA200801806A ZA200801806B (en) | 2007-03-06 | 2008-02-26 | Method of treating of zinc- and germanium containing solid-phase polymetallic mineral material |
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| ZA (1) | ZA200801806B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2423535C1 (en) * | 2010-04-27 | 2011-07-10 | Леонид Михайлович Черемисинов | Procedure for hydro-metallurgical treatment of minerals |
| CN106148690B (en) * | 2015-04-08 | 2018-06-29 | 贵州宏达环保科技有限公司 | A kind of germanium silicon separation method |
| CN104862500A (en) * | 2015-06-03 | 2015-08-26 | 云南天浩稀贵金属股份有限公司 | Metal germanium recovery device and metal germanium recovery method |
| RU2658546C2 (en) * | 2016-09-09 | 2018-06-21 | Елена Алексеевна Строганова | Method for processing a zinc and copper-containing polymetallic mineral material |
| CN108130431B (en) * | 2017-12-04 | 2019-09-20 | 云南驰宏资源综合利用有限公司 | A kind of method that richness germanium zinc concentrate oxygen leaching inhibits germanium to leach |
| CN115058607A (en) * | 2022-07-26 | 2022-09-16 | 广东先导稀材股份有限公司 | Method for enriching germanium from germanium-containing solution |
| CN116732356B (en) * | 2023-08-15 | 2023-10-03 | 昆明理工大学 | Method for synchronously leaching and precipitating germanium in zinc suboxide smoke dust |
| CN116875826B (en) * | 2023-09-07 | 2023-11-14 | 昆明理工大学 | Method for extracting germanium by zinc oxide smoke depth and short process |
-
2007
- 2007-03-06 RU RU2007108704/02A patent/RU2337164C1/en not_active IP Right Cessation
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2008
- 2008-02-26 ZA ZA200801806A patent/ZA200801806B/en unknown
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| RU2337164C1 (en) | 2008-10-27 |
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