CN114921665B - Method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by extraction method - Google Patents
Method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by extraction method Download PDFInfo
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Abstract
The invention provides a method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by an extraction method, which belongs to the technical field of resource regeneration and comprises the processes of preparation of an extracted organic phase, preparation of germanium-containing extract, extraction separation, back extraction, germanium precipitation enrichment and the like.
Description
Technical Field
The invention relates to the technical field of germanium resource regeneration, in particular to a method for regenerating germanium and hydrochloric acid from a germanium-containing hydrochloric acid solution by an extraction method.
Background
Germanium is a high-value rare metal with extremely rare earth content, an important semiconductor material, and is globally held in an amount of about 8600 tons, and germanium is currently being listed as a strategic metal in multiple countries. Germanium is mainly used in the fields of infrared material production, photovoltaic industry, optical fiber industry, PET catalysis industry, food and medicine production and the like. Germanium has wide application in the high and new technical fields of new energy sources, infrared optics, optical fibers, catalysts, electronics, solar energy and the like, and is an important resource for the development of strategically emerging industries.
The germanium has low metal direct yield in the production process because of complex process; because of high value and scarcity, the comprehensive recovery of germanium in the production process is indispensable and significant. The production process of the high-purity germanium dioxide comprises the processes of distillation, re-distillation, rectification, hydrolysis, washing, drying and the like, and because the germanium tetrachloride and the high-purity germanium dioxide have certain solubility in aqueous solution or hydrochloric acid solution, the wastewater generated in the whole production process of the high-purity germanium dioxide contains HCL and germanium, and the solutions related by the invention comprise 3 kinds of solutions as follows: firstly, the waste acid of a germanium tetrachloride condensing system in the processes of germanium distillation, re-distillation and the like contains 50-150 ug/mL of germanium and 7-11 mol/L of HCL; secondly, the re-steaming residual acid of the germanium re-steaming process contains 50 to 150 ug/mL germanium and 6.0 to 7.5mol/L HCL; thirdly, the washing water after the hydrolysis of the high-purity germanium dioxide contains 100 to 600 ug/mL germanium and 0.2 to 1mol/L HCL.
The method for recycling germanium from the above 3 germanium-containing hydrochloric acid solutions is mainly to neutralize hydrochloric acid in the solution with alkali and then to precipitate and enrich germanium by a tannin germanium precipitation method, a zinc substitution method, a germanium precipitation agent coprecipitation method and the like. The common disadvantage of the above methods is that the hydrochloric acid in the solution is neutralized with a large amount of alkali, which wastes hydrochloric acid and also increases the neutralization cost of alkali; the content of germanium in the solution is generally less than 600 ug/mL, the grade of regenerated and recovered germanium concentrate is lower, the content of germanium is generally less than 5%, and the subsequent germanium purification cost is increased; in addition, because tannic acid, zinc and the like are used, the cost and pressure of environmental protection treatment of the recovery system are greatly increased.
Aiming at the defects of the traditional process technology, the project plan develops a new technical scheme which is low in cost, high in efficiency, simple in flow, capable of synchronously recycling germanium and hydrochloric acid and higher in enrichment ratio of the germanium.
Disclosure of Invention
The invention aims to solve the defects existing in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by an extraction method comprises the following steps:
s1: preparation of an extracted organic phase: the extractant butyl acetate, the modifier tributyl phosphate and the diluent sulfonated kerosene are fully stirred and mixed to be used as an extraction organic phase.
S2: preparing germanium-containing extract: the three germanium-containing hydrochloric acid solutions of waste absorption acid, re-steaming residual acid and washing water for hydrolyzing germanium dioxide generated in the production process of high-purity germanium dioxide are fully stirred and mixed to be used as germanium-containing extract.
S3: and (3) extraction and separation: mixing the extracted organic phase obtained in the step S1 and the germanium-containing extract obtained in the step S2, stirring, standing for phase separation, and allowing germanium to enter the organic phase, wherein the aqueous phase is a pure hydrochloric acid solution, and the content of metal impurities is very low.
S4: back extraction: mixing the germanium-containing organic phase obtained in the step S3 with dilute hydrochloric acid, stirring, standing for phase separation, and allowing germanium in the organic phase to enter into a dilute hydrochloric acid solution, wherein the germanium is enriched in a water phase; the organic phase is regenerated and returned to S3 for recycling.
S5: concentration of germanium precipitation: adding alkali into the diluted hydrochloric acid solution containing germanium obtained in the step S4 to adjust the pH value, adding a compound germanium precipitating agent to precipitate germanium, and carrying out solid-liquid separation to obtain germanium concentrate.
Preferably, in S1, the volume ratio of the extractant butyl acetate, the modifier tributyl phosphate and the diluent sulfonated kerosene is 10-15:0.5-1:84-89.5.
Preferably, in S2, the volume ratio of the mixture of the waste absorption acid, the re-evaporation residual acid and the washing water for hydrolyzing germanium dioxide is 10-20:50-70:10-40, wherein the 3 germanium-containing hydrochloric acid solutions are generated in the production process of the high-purity germanium dioxide.
Preferably, in S2, the molar concentration of HCL in the prepared germanium-containing extract is controlled to be 5.5-6.5 mol/L.
Preferably, in S3, the ratio of the extracted aqueous phase to the organic phase, i.e. the volume ratio, is 3-5:1; extracting for 2-3 min; standing for 8-10 min.
Preferably, in S4, the molar concentration of HCL in the dilute hydrochloric acid for stripping is controlled to be 0.2-0.5 mol/L.
Preferably, in S4, the volume ratio of the stripping water phase to the organic phase is 1:3-5; the back extraction time is 5-8 min; standing for 8-10 min.
Preferably, in S5, caustic soda flakes or calcined soda is used to adjust the pH value of the solution to 7.5-8.5; the total mass of the added ferric chloride and magnesium chloride is 6-8 times of the total mass of germanium in the solution; the mass ratio of the added ferric chloride to the magnesium chloride is 1.5-2:1.
Compared with the prior art, the invention has the beneficial effects that: the extraction method is adopted to regenerate germanium and hydrochloric acid from the germanium-containing hydrochloric acid solution, so that the recovery rate of the germanium is greatly improved and the regeneration cost of the germanium is reduced while the germanium and the hydrochloric acid are fully recycled. The extraction rate and the back extraction rate of the butyl acetate extractant on germanium are both up to more than 99 percent; the concentration ratio of germanium in the whole process from the germanium-containing solution to the germanium concentrate is more than 500 times; germanium and hydrochloric acid are fully regenerated, the whole process is environment-friendly, and waste minimization is achieved; the regeneration process is short, the process is simple, the regeneration cost of germanium is less than 20 yuan/kgGe, and the direct yield of germanium is more than 92%.
Detailed Description
For a further understanding of the objects, construction, features, and functions of the invention, reference should be made to the following detailed description of the preferred embodiments.
The invention provides a method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by an extraction method, which comprises the following steps:
s1: preparation of an extracted organic phase: the extractant butyl acetate, the modifier tributyl phosphate and the diluent sulfonated kerosene are fully stirred and mixed to be used as an extraction organic phase.
S2: preparing germanium-containing extract: the three germanium-containing hydrochloric acid solutions of waste absorption acid, re-steaming residual acid and washing water for hydrolyzing germanium dioxide generated in the production process of high-purity germanium dioxide are fully stirred and mixed to be used as germanium-containing extract.
S3: and (3) extraction and separation: mixing the extracted organic phase obtained in the step S1 and the germanium-containing extract obtained in the step S2, stirring, standing for phase separation, and enabling germanium to enter the organic phase; the aqueous phase is a pure hydrochloric acid solution, has low metal impurity content, can be used for metal surface corrosion treatment, indium production and the like, and can also be sold as regenerated hydrochloric acid.
S4: back extraction: mixing the germanium-containing organic phase obtained in the step S3 with dilute hydrochloric acid, stirring, standing for phase separation, and allowing germanium in the organic phase to enter into a dilute hydrochloric acid solution, wherein the germanium is enriched in a water phase; the organic phase is regenerated and returned to S3 for recycling;
s5: concentration of germanium precipitation: adding alkali into the germanium-containing dilute hydrochloric acid solution obtained in the step S4 to adjust the pH value, adding a composite germanium precipitating agent to precipitate germanium, and carrying out solid-liquid separation to obtain germanium concentrate, wherein the germanium concentrate can be directly sold or sold after a high-purity germanium dioxide product is produced by a conventional process.
Preferably, in S1, the volume ratio of the extractant butyl acetate, the modifier tributyl phosphate and the diluent sulfonated kerosene is 10-15:0.5-1:84-89.5.
Preferably, in S2, the volume ratio of the mixture of the waste absorption acid, the re-evaporation residual acid and the washing water for hydrolyzing germanium dioxide is 10-20:50-70:10-40, wherein the 3 germanium-containing hydrochloric acid solutions are generated in the production process of the high-purity germanium dioxide.
Preferably, in S2, the molar concentration of HCL in the prepared germanium-containing extract is controlled to be 5.5-6.5 mol/L.
Preferably, in S3, the ratio of the extracted aqueous phase to the organic phase, i.e. the volume ratio, is 3-5:1; extracting for 2-3 min; standing for 8-10 min.
Preferably, in S4, the molar concentration of HCL in the dilute hydrochloric acid for stripping is controlled to be 0.2-0.5 mol/L.
Preferably, in S4, the volume ratio of the stripping water phase to the organic phase is 1:3-5; the back extraction time is 5-8 min; standing for 8-10 min.
Preferably, in S5, caustic soda flakes or calcined soda is used to adjust the pH value of the solution to 7.5-8.5; the total mass of the added ferric chloride and magnesium chloride is 6-8 times of the total mass of germanium in the solution; the mass ratio of the added ferric chloride to the magnesium chloride is 1.5-2:1.
The invention adopts the extraction organic phase prepared by S1, wherein the butyl acetate can effectively extract elements such as germanium, trivalent arsenic, trivalent iron and the like in a hydrochloric acid system; tributyl phosphate can effectively reduce the emulsification of an extracted organic phase and accelerate the phase separation speed of extraction; the addition of sulfonated kerosene can improve the physical properties of the extracted organic phase, such as reducing the viscosity of the extractant to increase the fluidity thereof, changing the density of the organic phase, expanding the density difference between the oil phase and the water phase, and being beneficial to the separation and clarification of the two phases.
According to the invention, the preparation of the germanium-containing extract is carried out through S2, when the molar concentration of HCL in the solution in the extraction process is more than 5mol/L, the butyl acetate has high extraction rate on germanium, but when the molar concentration of HCL in the solution is more than 7mol/L, the butyl acetate can be partially decomposed, so that the molar concentration of HCL in the mixed solution is controlled to be 5.5-6.5mol/L, the butyl acetate has high extraction rate on germanium, and the butyl acetate can be prevented from being decomposed. The waste acid of germanium tetrachloride condensing system in germanium distillation, re-evaporation and other processes is absorbed, wherein the waste acid contains 50-150 ug/mL germanium and 7-11 mol/L HCL, and if the waste acid is extracted singly, more decomposition loss of butyl acetate can be generated; the re-steaming residual acid of the germanium re-steaming process contains 50-150 ug/mL germanium and 6.0-7.5 mol/L HCL, and if the residual acid is extracted singly, a small amount of butyl acetate is lost; the washing water for hydrolyzing germanium dioxide contains 100-600 ug/mL germanium and 0.2-1 mol/L HCL, and if the washing water is extracted singly, the germanium can not be extracted by butyl acetate basically because of low HCL molar concentration in the solution; therefore, the 3 solutions are mixed to prepare the mixed solution, so that the molar concentration of HCL in the mixed solution is in a preferred range of 5.5-6.5mol/L, and the loss of butyl acetate is minimized while the high extraction rate is achieved.
The invention fully extracts germanium and a small amount of impurities in the germanium-containing extract into an organic phase through S3 extraction and separation, simultaneously purifies hydrochloric acid solution, ensures that the molar concentration of HCL in a water phase after extraction and separation is 5.4-6.4 mol/L, can be used for metal surface corrosion and indium production, and can also be sold as regenerated hydrochloric acid.
The invention uses the characteristic that germanium enters into an organic phase containing butyl acetate when the acidity of hydrochloric acid is high and enters into a water phase when the acidity of hydrochloric acid is low to control the back extraction liquid to be low acidity and small volume, and can back extract the germanium into a dilute hydrochloric acid solution and enrich the germanium. The back extraction liquid is compared with the germanium-containing extraction liquid, and the enrichment ratio of germanium is more than 10 times.
The invention uses S5 to neutralize free small amount of HCL in the back extraction liquid with caustic soda flakes or sodium carbonate, uses the mixture of ferric salt and magnesium salt as compound germanium precipitating agent, uses the characteristic that germanate of heavy metal and alkaline earth metal is indissolvable in water, generates ferric germanate and magnesium germanate precipitate in solution, and ferric hydroxide colloid formed by excessive iron can adsorb germanium to form coprecipitation, thus obtaining germanium concentrate with germanium content more than 10%.
Example 1
S1: preparation of an extracted organic phase: the extractant butyl acetate, the modifier tributyl phosphate and the diluent sulfonated kerosene are mixed according to the volume ratio of 10:0.5:84, and the mixture is fully stirred and mixed to be used as an extraction organic phase.
S2: preparing germanium-containing extract: mixing three germanium-containing hydrochloric acid solutions, namely waste absorption acid, re-evaporation residual acid and washing water for hydrolyzing germanium dioxide, generated in the production process of high-purity germanium dioxide in a certain factory according to the volume ratio of 10:50:10, and fully stirring and mixing to obtain germanium-containing extract, wherein the molar concentration of HCL in the prepared germanium-containing extract is controlled to be 5.5-6.5 mol/L.
S3: and (3) extraction and separation: mixing the extracted organic phase obtained in the step S1 and the germanium-containing extract liquid obtained in the step S2 according to the volume ratio of 3:1, stirring, standing and phase-separating; extracting for 2min; standing for 8min.
S4: back extraction: mixing the germanium-containing organic phase obtained in the step S3 with a dilute hydrochloric acid solution with the molar concentration of 0.2mol/L, stirring, standing and phase-separating; the volume ratio of the stripping water phase to the organic phase is 1:3; the back extraction time is 5min; standing for 8min.
S5: concentration of germanium precipitation: adding caustic soda flakes or sodium carbonate into the germanium-containing dilute hydrochloric acid solution obtained in the step S4 to adjust the pH value of the solution to 7.5, adding a compound germanium precipitating agent of ferric chloride and magnesium chloride to precipitate germanium, wherein the total mass of the added ferric chloride and magnesium chloride is 6 times of the total mass of germanium in the solution; the mass ratio of the added ferric chloride to the magnesium chloride is 1.5:1.
By the extraction method of this example, the direct yield of final germanium was 92.78%.
Example 2
S1: preparation of an extracted organic phase: the extractant butyl acetate, the modifier tributyl phosphate and the diluent sulfonated kerosene are mixed according to the volume ratio of 13:0.75:87, and the mixture is fully stirred and mixed to be used as an extraction organic phase.
S2: preparing germanium-containing extract: mixing and fully stirring three germanium-containing hydrochloric acid solutions, namely waste absorption acid, re-evaporation residual acid and washing water for hydrolyzing germanium dioxide, generated in the production process of high-purity germanium dioxide in a certain factory according to the volume ratio of 15:60:25 to obtain germanium-containing extract, wherein the molar concentration of HCL in the prepared germanium-containing extract is controlled to be 5.5-6.5 mol/L.
S3: and (3) extraction and separation: mixing the extracted organic phase obtained in the step S1 and the germanium-containing extract liquid obtained in the step S2 according to the volume ratio of 4:1, stirring, standing and phase-separating; extracting for 3min; standing for 10min.
S4: back extraction: mixing the germanium-containing organic phase obtained in the step S3 with a dilute hydrochloric acid solution with the molar concentration of 0.35mol/L, stirring, standing and phase-separating; the volume ratio of the stripping water phase to the organic phase is 1:4; the back extraction time is 8min; standing for 10min.
S5: concentration of germanium precipitation: adding caustic soda flakes or sodium carbonate into the germanium-containing dilute hydrochloric acid solution obtained in the step S4 to adjust the pH value of the solution to 8.0, adding a compound germanium precipitating agent of ferric chloride and magnesium chloride to precipitate germanium, wherein the total mass of the added ferric chloride and magnesium chloride is 8 times of the total mass of germanium in the solution; the mass ratio of the added ferric chloride to the magnesium chloride is 2:1.
By the extraction method of this example, the direct yield of final germanium was 92.95%.
Example 3
S1: preparation of an extracted organic phase: the extractant butyl acetate, the modifier tributyl phosphate and the diluent sulfonated kerosene are mixed according to the volume ratio of 15:1:89.5, and the mixture is fully stirred and mixed to be used as an extraction organic phase.
S2: preparing germanium-containing extract: mixing and fully stirring three germanium-containing hydrochloric acid solutions, namely waste absorption acid, re-evaporation residual acid and washing water for hydrolyzing germanium dioxide, generated in the production process of high-purity germanium dioxide in a certain factory according to the volume ratio of 20:70:40 to obtain germanium-containing extract, wherein the molar concentration of HCL in the prepared germanium-containing extract is controlled to be 5.5-6.5 mol/L.
S3: and (3) extraction and separation: mixing the extracted organic phase obtained in the step S1 and the germanium-containing extract liquid obtained in the step S2 according to the volume ratio of 5:1, stirring, standing and phase-separating; extracting for 3min; standing for 10min.
S4: back extraction: mixing the germanium-containing organic phase obtained in the step S3 with a dilute hydrochloric acid solution with the molar concentration of 0.35mol/L, stirring, standing and phase-separating; the volume ratio of the stripping water phase to the organic phase is 1:5; the back extraction time is 8min; standing for 10min.
S5: concentration of germanium precipitation: adding caustic soda flakes or sodium carbonate into the germanium-containing dilute hydrochloric acid solution obtained in the step S4 to adjust the pH value of the solution to 8.5, adding a compound germanium precipitating agent of ferric chloride and magnesium chloride to precipitate germanium, wherein the total mass of the added ferric chloride and magnesium chloride is 8 times of the total mass of germanium in the solution; the mass ratio of the added ferric chloride to the magnesium chloride is 2:1.
By the extraction method of this example, the direct yield of final germanium was 92.91%.
By the method, the recovery rate of germanium is greatly improved and the regeneration cost of germanium is reduced while fully recycling the germanium and the hydrochloric acid. The extraction rate and the back extraction rate of the butyl acetate extractant on germanium are both up to more than 99 percent; the concentration ratio of germanium in the whole process from the germanium-containing solution to the germanium concentrate is more than 500 times; germanium and hydrochloric acid are fully regenerated, the whole process is environment-friendly, and waste minimization is achieved; the regeneration process is short, the process is simple, the regeneration cost of germanium is less than 20 yuan/kgGe, and the direct yield of germanium is more than 92%.
The invention has been described with respect to the above-described embodiments, however, the above-described embodiments are merely examples of practicing the invention. It should be noted that the disclosed embodiments do not limit the scope of the invention. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (6)
1. A method for regenerating germanium and hydrochloric acid from germanium-containing hydrochloric acid solution by an extraction method is characterized in that: the method comprises the following steps:
s1: preparation of an extracted organic phase: fully stirring and mixing extractant butyl acetate, modifier tributyl phosphate and diluent sulfonated kerosene to obtain an extracted organic phase;
s2: preparing germanium-containing extract: fully stirring and mixing three germanium-containing hydrochloric acid solutions, namely waste absorption acid, re-steaming residual acid and washing water for hydrolyzing germanium dioxide, generated in the production process of high-purity germanium dioxide, to obtain a germanium-containing extract, wherein the molar concentration of HCL in the prepared germanium-containing extract is controlled to be 5.5-6.5mol/L;
s3: and (3) extraction and separation: mixing the extracted organic phase obtained in the step S1 and the germanium-containing extract obtained in the step S2, stirring, standing for phase separation, wherein germanium enters the organic phase, the aqueous phase is a pure hydrochloric acid solution, and the metal impurity content is very low;
s4: back extraction: mixing the germanium-containing organic phase obtained in the step S3 with dilute hydrochloric acid, stirring, standing for phase separation, and allowing germanium in the organic phase to enter into a dilute hydrochloric acid solution, wherein the germanium is enriched in a water phase; the organic phase is regenerated and returned to S3 for recycling; the molar concentration of HCL in the dilute hydrochloric acid for back extraction is controlled to be 0.2-0.5mol/L;
s5: concentration of germanium precipitation: adding alkali into the diluted hydrochloric acid solution containing germanium obtained in the step S4 to adjust the pH value, adding a compound germanium precipitating agent to precipitate germanium, and carrying out solid-liquid separation to obtain germanium concentrate.
2. The method for regenerating germanium and hydrochloric acid from a germanium-containing hydrochloric acid solution according to claim 1, wherein the method comprises the steps of: in S1, the volume ratio of the extractant butyl acetate, the modifier tributyl phosphate and the diluent sulfonated kerosene is 10-15:0.5-1:84-89.5.
3. The method for regenerating germanium and hydrochloric acid from a germanium-containing hydrochloric acid solution according to claim 1, wherein the method comprises the steps of: in S2, the volume ratio of the mixture of the waste absorption acid, the redistilled residual acid and the washing water for hydrolyzing germanium dioxide is 10-20:50-70:10-40, wherein the 3 germanium-containing hydrochloric acid solutions are generated in the production process of the high-purity germanium dioxide.
4. The method for regenerating germanium and hydrochloric acid from a germanium-containing hydrochloric acid solution according to claim 1, wherein the method comprises the steps of: in S3, the volume ratio of the extracted water phase to the organic phase is 3-5:1; extracting for 2-3 min; standing for 8-10 min.
5. The method for regenerating germanium and hydrochloric acid from a germanium-containing hydrochloric acid solution according to claim 1, wherein the method comprises the steps of: in S4, the volume ratio of the stripping water phase to the organic phase is 1:3-5; the back extraction time is 5-8 min; standing for 8-10 min.
6. The method for regenerating germanium and hydrochloric acid from a germanium-containing hydrochloric acid solution according to claim 1, wherein the method comprises the steps of: in S5, adjusting the pH value of the solution to 7.5-8.5 by using caustic soda flakes or sodium carbonate; the total mass of the added ferric chloride and magnesium chloride is 6-8 times of the total mass of germanium in the solution; the mass ratio of the added ferric chloride to the magnesium chloride is 1.5-2:1.
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| CN114277264A (en) * | 2021-12-28 | 2022-04-05 | 广东先导稀材股份有限公司 | Method for extracting and recovering germanium |
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