CN115109950A - Method for producing germanium concentrate by back extraction from hydroxamic acid loaded organic phase - Google Patents

Method for producing germanium concentrate by back extraction from hydroxamic acid loaded organic phase Download PDF

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CN115109950A
CN115109950A CN202210662226.2A CN202210662226A CN115109950A CN 115109950 A CN115109950 A CN 115109950A CN 202210662226 A CN202210662226 A CN 202210662226A CN 115109950 A CN115109950 A CN 115109950A
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germanium
solution
organic phase
back extraction
alkaline
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CN115109950B (en
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张伟
宫晓丹
张俊峰
吴才贵
黄青
胡立
高艳芬
郑莉莉
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Shenzhen Zhongjin Lingnan Nonfemet Co ltd
Danxia Smelter Of Shenzhen Zhongjin Lingnan Nonfemet Co ltd
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Shenzhen Zhongjin Lingnan Nonfemet Co ltd
Danxia Smelter Of Shenzhen Zhongjin Lingnan Nonfemet Co ltd
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Abstract

The invention relates to a method for producing germanium concentrate by back extraction from a hydroxamic acid loaded organic phase. The method comprises the following steps: s1 back extraction: mixing and extracting alkaline ammonium tartrate aqueous solution serving as a stripping agent and a germanium-containing hydroxamic acid loaded organic phase to obtain a germanium-containing stripping solution and a stripped organic phase; s2 germanium precipitation: mixing and neutralizing the germanium-containing back extraction solution and an alkaline reagent, and performing solid-liquid separation to obtain a germanium-containing precipitate and a germanium-precipitated solution; s3 calcination: and (4) calcining and crushing the germanium-containing precipitate obtained in the step (S2) to obtain germanium concentrate, and absorbing calcined tail gas by an acid solution until the calcined tail gas reaches the standard and is discharged. The method has the advantages of low consumption of the stripping agent and difficult generation of sediment in the stripping process to cause pipeline blockage.

Description

Method for producing germanium concentrate by back extraction from hydroxamic acid loaded organic phase
Technical Field
The invention relates to the field of scattered germanium metal recovery, in particular to a back extraction process for extracting germanium from a hydroxamic acid loaded organic phase.
Background
Since the discovery of the 19 th century, germanium has been widely used in the fields of semiconductors, aerospace measurement and control, nuclear physics detection, optical fiber communication, infrared optics, solar cells, chemical catalysts, biomedicine, and the like due to its unique physicochemical properties. However, germanium is a rare metal, and most of germanium exists in silicate and metal ore in a rare state in the earth crust, and because the grade of germanium in the germanium-containing ore and slag thereof is low, the extraction and recovery of germanium are difficult. At present, the methods for extracting and recovering germanium mainly comprise a precipitation method, an ion exchange method, an extraction method and the like.
Among them, the extraction method is the most widely used method for extracting and recovering germanium at present. At present, extracting agents for extracting and recovering germanium by an extraction method can be generally divided into three types, namely hydroxyoxime type and quinoline type; secondly, amine extractant; thirdly, hydroxamic acid extractant. The main products of the hydroxamic acid extractants which are commonly used at present are YW100, 7815, H106, HGS98, G315, G8315 and the like. The hydroxamic acid extractant is not used for extracting germanium alone, other extractants are added to form a synergistic extractant system, and the used extractants mainly comprise P204, N235, fatty acid and the like, and are generally most widely applied as P204. After the germanium is extracted by the extraction method, the germanium needs to be back extracted from the loaded organic phase to further prepare germanium concentrate with higher purity.
At present, the stripping agents for stripping germanium from the loaded organic phase comprise ammonium sulfate, hydrofluoric acid, sodium hydroxide, ammonium fluoride, perchloric acid, hypochlorous acid, ammonium tartrate and the like, wherein the ammonium sulfate system has low stripping efficiency and is less used in production; perchloric acid and hypochlorous acid are less frequently used; the back extraction effect of mainly hydrofluoric acid and ammonium fluoride is good, but the germanium enrichment solution contains fluorine, so that the problems of low safety, serious corrosion, large environmental pollution, poor product quality and the like are caused; ammonium tartrate as a stripping agent can avoid the problems, but the consumption of the stripping agent is high in the stripping process, precipitates are easily generated to cause the blockage of an extraction box pipeline, extraction flow is cut off in serious cases, and the ammonium tartrate needs to be cleaned regularly, so that the production cost is increased.
Therefore, there is a great need for improvements in germanium extraction processes using ammonium tartrate as stripping agent.
Disclosure of Invention
Based on the above, the invention aims to provide a method for producing germanium concentrate by stripping from a hydroxamic acid loaded organic phase, which has the advantages of high safety and low consumption of stripping agent.
A method for producing germanium concentrate by back extraction from a hydroxamic acid loaded organic phase comprises the following steps:
s1 back extraction: mixing and extracting alkaline ammonium tartrate aqueous solution serving as a stripping agent and a germanium-containing hydroxamic acid loaded organic phase to obtain a germanium-containing stripping solution and a stripped organic phase;
s2 germanium precipitation: mixing and neutralizing the germanium-containing back extraction solution and an alkaline reagent, and performing solid-liquid separation to obtain a germanium-containing precipitate and a germanium-precipitated solution;
s3 calcination: and (4) calcining and crushing the precipitate obtained in the step (S2) to obtain germanium concentrate, and absorbing the calcined tail gas by an acid solution until the calcined tail gas reaches the standard and is discharged.
The scheme has the advantages of low consumption of the stripping agent in the stripping process, no precipitate generated in the stripping process, no need of regular cleaning and no fluorine-containing stripping product.
Further, the alkaline reagent in step S2 is an alkaline ammonia reagent, and the germanium precipitation solution obtained in step S2 is returned to step S1 to be used as a stripping agent. The scheme has the advantages that ammonia gas is not volatilized in the germanium precipitation process, precipitates are easy to process, and the obtained germanium concentrate is high in germanium grade.
Further, the method also comprises the step of processing the organic phase after the back extraction in the step S4: and (4) washing the stripped organic phase generated in the step S1 by using pure water, using the washed regenerated organic phase as an extracting agent, and using the washing solution after being concentrated as a preparation raw material of the stripping agent. Wherein the extractant is used for extracting and recovering germanium by an extraction method. The scheme has the advantages that no precipitate is generated in the washing process, and the washing liquid can be recycled, so that the production cost is reduced.
Further, the acid solution in the step S3 is a tartaric acid solution, and the concentration of the tartaric acid solution is 50-250 g/L.
Further, the method also comprises the step of S0 preparing a stripping agent: adding an alkaline ammonia reagent into the ammonium tartrate aqueous solution to adjust the solution to be alkaline, thereby obtaining a stripping agent; wherein the concentration of the ammonium tartrate aqueous solution is 0.25-3 mol/L.
Further, in the step S3, the tartaric acid solution absorbs the tail gas until the pH value reaches 1-5, the solution is replaced and the precipitated precipitate is cleaned, the solution and the precipitated precipitate are subjected to solid-liquid separation to obtain an absorbed solution and a filter residue, the absorbed solution is used as a raw material of the tartaric acid solution in the step S3, and the filter residue is used as a raw material for preparing the stripping agent in the step S0. The scheme has the advantages that the tail gas can be recycled, the step of treating hazardous waste residues generated after absorption in the traditional process is omitted, the production cost is reduced, and the environment is protected.
Further, the volume ratio of the organic phase to the pure water after the back extraction in the step S4 is 4: 1-20: 1, the number of extraction stages is 2-5, the extraction time is 2-15 minutes, and the temperature is 25-65 ℃.
Further, the alkaline ammonia reagent in step S0 and/or the alkaline ammonia reagent in step S3 is one of ammonia water, ammonium carbonate, and liquid ammonia.
Further, the pH value of the stripping agent obtained in the step S0 is 7.5-9.5.
Further, in the step S1, the volume ratio of the germanium-containing hydroxamic acid loaded organic phase to the stripping agent is 1: 1-15: 1, the number of stripping stages is 2-5, the extraction time is 2-15 minutes, and the temperature is 25-65 ℃.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic flow diagram of the method for producing germanium concentrate by stripping from hydroxamic acid loaded organic phase according to the present invention.
Detailed Description
The method analyzes the back extraction process aiming at the problems of high consumption of the back extractant, more precipitates generated in the back extraction process and easy blockage of an extraction box pipeline in the process of extracting germanium from the hydroxamic acid loaded organic phase by taking the ammonium tartrate solution as the back extractant in the prior art.
In the conventional preparation of germanium concentrate, the germanium-containing sulfuric acid solution and hydroxamic acid are chelated to realize extraction, and germanium and an extracting agent hydroxamic acid generate a stable complex, namely a hydroxamic acid loaded organic phase. During the process of back extraction of germanium from the hydroxamic acid loaded organic phase, ammonium tartrate reacts with germanium to generate a more stable ammonium germanium tartrate complex, and the ammonium germanium tartrate complex enters the water phase to realize back extraction. Because the organic phase obtained after extracting germanium from the germanium-containing sulfuric acid solution by the hydroxamic acid carries a small amount of acid-containing feed liquid or acid-containing washing liquid, and the hydroxamic acid is released in the process of back extracting germanium from the hydroxamic acid loaded organic phase by using the ammonium tartrate solution, hydrogen ions ionized from the small amount of acid in the back extraction process compete with excessive ammonium tartrate ions in a back extractant, namely one hydrogen ion replaces one ammonium ion in a molecule, and the following side reaction occurs:
(NH 4 ) 2 C 4 H 4 O 6 +H + ＝NH 4 HC 4 H 4 O 6 +NH 4 +
because the solubility (the solubility at 20 ℃ is 2.7g/100g water) of ammonium bitartrate generated by the side reaction is obviously lower than that of ammonium bitartrate (the solubility at 20 ℃ is 63g/100g water), saturated ammonium bitartrate can be separated out and deposited at the bottom of the clarifying tank and an overflow weir of a mixing chamber in the process, so that the pipeline of the extracting tank is blocked, extraction flow can be cut off seriously, the separated ammonium bitartrate can not have the effect of back extraction any more, the consumption of the ammonium bitartrate is increased, the production cost is increased, and an extracting system needs to be cleaned regularly.
Aiming at the analysis, the stripping agent is replaced by a basic ammonium tartrate aqueous solution from a conventional ammonium tartrate aqueous solution (the pH value of the ammonium tartrate aqueous solution ranges from 6.0 to 7.0).
At this time, because the back extraction process is carried out in an alkaline environment, acid carried in the organic phase and hydroxamic acid released after back extraction of germanium firstly respectively undergo neutralization reaction and saponification reaction with alkali to generate corresponding salt and ammonium hydroxamate, thereby preventing the ammonium tartrate from being converted into ammonium hydrogen tartrate.
Further optimally, the stripping agent may be an aqueous solution of ammonium tartrate with the pH adjusted to basic using a basic ammonia reagent. At this time, because the environment has excessive alkaline ammonia reagent, if part of ammonium hydrogen tartrate is still separated out in the back extraction process, the ammonium hydrogen tartrate will be dissolved and converted into ammonium tartrate again when meeting a small amount of alkaline ammonia reagent, namely, ammonium ions replace the hydrogen ions, and the process is the reverse reaction of the above side reaction, and the reaction is as follows:
NH 4 HC 4 H 4 O 6 +NH 4 + ＝(NH 4 ) 2 C 4 H 4 O 6 +H +
therefore, the stripping agent is replaced by the alkaline ammonium tartrate aqueous solution from the conventional ammonium tartrate aqueous solution, and particularly, the improvement of the ammonium tartrate aqueous solution by using the alkaline ammonia reagent to adjust the pH value to be alkaline can effectively inhibit the problem of precipitation in the ammonium tartrate stripping process and improve the utilization efficiency of the stripping agent. Wherein the alkaline ammonia reagent is preferably one of ammonia water, ammonium carbonate and liquid ammonia.
For the germanium precipitation step, the alkaline reagent may be one of common alkaline reagents such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, etc., which all react with the strip liquor to generate germanium-containing precipitate. However, the addition of strong alkali such as sodium hydroxide and potassium hydroxide causes ammonia gas volatilization in the germanium precipitation process, so that an exhaust gas treatment process is required to be added, and the addition of a reagent such as sodium carbonate causes difficulty in removing ammonium when the germanium-containing precipitate is calcined subsequently, so that the quality of the germanium concentrate is affected, so that the alkaline reagent is preferably an alkaline ammonia reagent in the step. On one hand, the alkaline ammonia reagent can avoid the problems, on the other hand, the liquid components after germanium precipitation are simpler, and the liquid components can be directly returned to the back extraction step to be used as a back extractant, so that the consumption of the back extractant is further reduced. Further, the alkaline ammonia reagent is preferably one of ammonia water, ammonium carbonate and liquid ammonia.
The invention further uses tartaric acid solution as tail gas absorption liquid in the process of calcining the germanium-containing precipitate after germanium precipitation. Because the germanium ammonium tartrate is decomposed into germanium oxide, ammonia gas, carbon dioxide and other substances at high temperature in the calcination process of the germanium-containing precipitate, the decomposed ammonia gas can be absorbed by adopting the tartaric acid solution as an absorption liquid, and the ammonium hydrogen tartrate is generated in an acidic environment. The mixed liquid in the absorption tower is cleaned, the pH value of the absorbed liquid obtained after solid-liquid separation can be adjusted, and the absorbed liquid is continuously used as the absorption liquid, and the obtained ammonium hydrogen tartrate precipitate can be converted into ammonium tartrate by adding an alkaline ammonia reagent so as to be used as a preparation raw material of a back extractant. Therefore, by using the tartaric acid solution as the tail gas absorption liquid, on one hand, the waste gas emission can be reduced, on the other hand, ammonia gas can be recovered, and the resource utilization is realized.
On the other hand, the washing mode of the organic phase in the conventional method is changed from dilute sulfuric acid washing to pure water washing, so that the problem that ammonium hydrogen tartrate is separated out by the reaction of sulfuric acid and ammonium tartrate carried in the organic phase when the organic phase is washed by the conventional method, thereby increasing the consumption of the ammonium tartrate is solved, and the problems that the washing liquid obtained after the dilute sulfuric acid washing is complex in component, needs lime neutralization treatment and can generate a large amount of hazardous waste residues are also solved.
The following is a basic embodiment of the scheme of the invention, comprising the following steps:
preparation of an S0 stripping agent: adding ammonium tartrate into water, stirring and mixing until the ammonium tartrate is completely dissolved, and slowly adding an alkaline ammonia reagent into the solution until the solution is alkaline in the stirring process to obtain the stripping agent. Wherein the alkaline ammonia reagent is preferably one of ammonia water, ammonium carbonate and liquid ammonia.
S1 back extraction: mixing and extracting the stripping agent obtained in the step S0 and the germanium-containing hydroxamic acid loaded organic phase, and clarifying and separating to obtain a germanium-containing stripping solution and a stripped organic phase;
and respectively carrying out subsequent treatment on the germanium-containing strip liquor and the strip organic phase obtained in the step S1.
Wherein the treatment of the germanium-containing strip liquor comprises the following steps:
s2 germanium precipitation: pumping the germanium-containing back extraction solution into a reaction kettle, starting stirring, introducing an alkaline reagent at the bottom, filtering by a filter press after full absorption and neutralization to obtain germanium-containing precipitate and germanium-precipitating solution, and adding the germanium-precipitating solution into a germanium back extraction agent tank for recycling. The alkaline reagent is preferably an alkaline ammonia reagent, and further preferably one of ammonia water, ammonium carbonate, and liquid ammonia.
S3 calcination: and (4) adding the germanium-containing precipitate obtained in the step S2 into a calcining furnace for calcining, and absorbing tail gas by adopting tartaric acid solution in the calcining process. Crushing and packaging the calcined solid to obtain germanium concentrate. And (4) after solid-liquid separation of the absorbed liquid obtained after tail gas absorption and the precipitated precipitate, using the filtrate as a raw material of the tartaric acid solution in the step S4, and using the filter residue as a raw material for preparing the stripping agent in the step S1. The treatment of the organic phase after back extraction comprises the following steps:
and (3) organic phase treatment after S4 back extraction: and mixing and washing the organic phase obtained in the S1 after the back extraction with pure water, clarifying and separating to obtain a washing liquid of a water phase and a regenerated organic phase, wherein the regenerated organic phase can be recycled as an organic extractant of germanium.
S5 washing solution treatment: and (3) analyzing the tartaric acid content after the washing liquid is evaporated and concentrated, supplementing tartaric acid, adding ammonia water to adjust the pH value, and adding the solution into a germanium back-extraction agent tank for recycling. The condensed water evaporated in the process is used for extracting the organic phase after back extraction.
According to the above principle and basic embodiment, example 1 is set for comparison of the stripping process using the conventional tartaric acid solution and the basic ammonium tartrate solution as the stripping agent in step S1; examples 2 and 3 are respectively set for selection of different parameters in each step in the basic implementation mode; for the reuse methods of the filtrate and the residue in step S3, examples 4 and 5 were respectively provided.
Example 1
200mL of 2mol/L ammonium tartrate solution is prepared for later use.
100mL of germanium-loaded organic phase consisting of 5% of P204+ 2% of YW100+ 93% of solvent oil and 100mL of prepared 2mol/L ammonium tartrate solution are added into a 250mL beaker and mixed according to the volume ratio of 1:1 for 15 min. White precipitate was precipitated from the organic phase and the bottom of the beaker, the organic phase was separated with a separatory funnel, and the remaining solution and the precipitate were suction-filtered under negative pressure to obtain 17.06g of the precipitate.
And taking the rest prepared 2mol/L ammonium tartrate solution, adding ammonia water to adjust the pH value to 9.0, measuring 100mL by using a measuring cylinder, and mixing with the germanium-loaded organic phase, wherein the composition, the volume ratio and the mixing time of the germanium-loaded organic phase are the same as those of the experiment. The phase separation is good after the back extraction, and no precipitate is generated in an organic phase and a back extraction solution.
Example 2
One embodiment of the method for producing germanium concentrate by back extraction of hydroxamic acid loaded organic phase comprises the following steps:
preparation of an S0 stripping agent: adding 500kg ammonium tartrate into 1m3 aqueous solution, stirring and mixing until all ammonium tartrate is dissolved, and slowly adding ammonia water into the solution during stirring until the pH value is 9 to obtain the back extraction agent.
S1 back extraction: and (3) mixing the stripping agent obtained in the step (S1) with the germanium-containing hydroxamic acid loaded organic phase according to the volume ratio of 1:8, mixing for 5min, performing stripping at 4 levels and 45 ℃, and performing clarification and separation to obtain a germanium-containing stripping solution of a water phase and a stripped organic phase. At this time, the stripping solution was found to contain 6.4g/L of germanium and to have a pH of 7.8. Wherein the composition of the hydroxamic acid loaded organic phase is 10% of P204+ 5% of YW100+ 85% of solvent oil.
And respectively carrying out subsequent treatment on the germanium-containing strip liquor and the stripped organic phase obtained in the step S1, wherein the treatment on the germanium-containing strip liquor is as follows:
s2 germanium precipitation: pumping the germanium-containing stripping solution into a reaction kettle, starting stirring, introducing liquid ammonia at the bottom, fully absorbing and neutralizing until the pH value is 8.8, continuing the reaction for 1 hour, and filtering by a filter press to obtain 28kg of wet precipitate and germanium-precipitated solution. Analyzing to obtain 55% of moisture in the wet precipitate and 41% of germanium grade in the moisture-free solid; the content of germanium in the solution after germanium precipitation is 1.2g/L, the content of tartaric acid is 71.7g/L, and the solution after germanium precipitation is added into a germanium back-extraction agent groove for recycling.
S3 calcination: and (3) adding the wet precipitate obtained in the step (S2) into a baffle calcining furnace, setting the temperature to be 450 ℃, calcining for 4 hours, and absorbing tail gas by adopting tartaric acid solution with the concentration of 50g/L in the calcining process. Crushing and packaging the calcined solid to obtain 9.9kg of germanium concentrate, and analyzing to obtain 51.2% of germanium in the germanium concentrate; after absorbing tail gas, the absorption liquid can be added into a germanium back-extraction agent groove for cyclic utilization after being processed.
The organic phase after stripping is treated as follows:
and (3) organic phase treatment after S4 back extraction: and (3) mixing the organic phase obtained in the S1 after the back extraction with pure water according to the volume ratio of 4:1, washing for 5min at the temperature of 45 ℃ in 2 stages, and obtaining a washing liquid of a water phase and a regenerated organic phase after clarification and separation. The tartaric acid concentration in the wash was 3.9g/L at this point of analysis. The regenerated organic phase can be used as an organic extractant of germanium for recycling.
S5 washing solution treatment: after 13 times of washing liquid is evaporated and concentrated, the content of tartaric acid after analysis and concentration is 48.7g/L, tartaric acid is added until the concentration is 89.7g/L, ammonia water is added to adjust the pH value to be 8.2, and then the solution is added into a germanium back-extraction agent groove for recycling. The condensed water evaporated in this process was added to pure water in step S4 for washing the organic phase.
According to the method for producing the germanium concentrate, the recovery rate of germanium from the germanium-loaded organic phase to the germanium concentrate reaches 97.5 percent.
Example 3
This example is another embodiment of the present invention for producing germanium concentrate by stripping hydroxamic acid loaded organic phase, comprising the following steps:
preparation of an S0 stripping agent: adding 2500kg of ammonium tartrate into the aqueous solution of 5m3, stirring and mixing until the ammonium tartrate is completely dissolved, and slowly adding ammonia water into the solution until the pH value is 8.8 during stirring to obtain the stripping agent.
S1 back extraction: and (3) mixing the stripping agent obtained in the step (S0) with the germanium-loaded organic phase according to the volume ratio of 1:15, mixing for 5min, performing stripping at the level of 2, performing clarification separation at the temperature of 35 ℃, and obtaining a germanium-containing stripping solution and a stripped organic phase. At this time, the stripping solution was analyzed to contain 5.4g/L of germanium. Wherein the composition of the hydroxamic acid loaded organic phase is 10% of P204+ 5% of YW100+ 85% of solvent oil.
And respectively carrying out subsequent treatment on the germanium-containing strip liquor and the strip-extracted organic phase obtained in the step S1, wherein the treatment on the germanium-containing strip liquor is as follows:
s2 germanium precipitation: pumping the germanium-containing stripping solution into a reaction kettle, starting stirring, introducing liquid ammonia at the bottom, fully absorbing and neutralizing until the pH value is 8.9, and filtering the solution through a filter press after reacting for 2 hours to obtain 140kg of wet precipitate and a solution after germanium precipitation. Analyzing to obtain the wet precipitate containing 60% of water and the moisture-free solid containing 40% of germanium grade; the content of germanium in the solution after germanium precipitation is 0.8g/L, the content of tartaric acid is 33.5g/L, and the solution after germanium precipitation is added into a germanium back-extraction agent groove for recycling.
S3 calcination: and (3) adding the wet precipitate obtained in the step (S2) into a baffle calcining furnace, setting the temperature at 500 ℃, calcining for 4 hours, and absorbing tail gas by adopting tartaric acid solution with the concentration of 50g/L in the calcining process. Crushing and packaging the calcined solid to obtain germanium concentrate, and analyzing 45.3kg of germanium concentrate containing 49.2% of germanium; the absorption liquid after absorbing the tail gas can be added into a germanium back-extraction agent groove for cyclic utilization after being processed.
The organic phase after stripping is treated as follows:
and (3) organic phase treatment after S4 back extraction: and (3) washing the organic phase obtained in the step (S1) after the back extraction and pure water for 5 grades, mixing for 5min, wherein the volume ratio of the organic phase to the pure water is 4:1, and the temperature is 35 ℃. And clarifying and separating to obtain a washing liquid and a regenerated organic phase. The tartaric acid concentration in the wash was 4.6g/L at this point of analysis. The regenerated organic phase can be used as an organic extractant of germanium for recycling.
S5 washing solution treatment: after the washing liquid is evaporated and concentrated by 12 times, the tartaric acid content is detected to be 51.5g/L, and the tartaric acid content is added into a germanium back-extraction agent groove for recycling. The condensed water evaporated in this process was added to pure water in step S4 for washing the organic phase.
According to the method for producing the germanium concentrate, the recovery rate of the germanium is 96.9 percent from the germanium-loaded organic phase to the germanium concentrate.
Example 4
This example is an implementation method of the step S4 of the present invention in which the tartaric acid solution for absorbing tail gas has a volume of 1.5m and the volume of the tartaric acid solution is taken as a raw material of the stripping agent 3 And spraying and absorbing tail gas by a circulating pump with the initial concentration of 50g/L, and pumping the absorption liquid in the absorption tower and the separated ammonium hydrogen tartrate mixed slurry into a filter press for circulating filtration when the pH value of the absorption liquid to be measured is 1.5 to finally obtain 128kg of ammonium hydrogen tartrate crystals. Wherein the pressure filtrate is returned to the absorption tower for cyclic utilization after tartaric acid is added, and ammonium hydrogen tartrate is crystallized and is 1.5m 3 Mixing and stirring water, slowly adding ammonia water, continuing stirring for 15min after the pH value of the solution reaches 9, measuring the tartaric acid concentration of the solution to be 44g/L, supplementing ammonium tartrate until the tartaric acid concentration is 100g/L, adjusting the pH value to be 9.5 by using ammonia water, and adding a germanium back-extraction agent storage tank for later use.
Example 5
This example is another method for implementing the absorbing tail gas and the precipitated precipitate as the stripping agent raw material in step S4, wherein the tartaric acid solution used for absorbing the tail gas has a volume of 1.5m 3 And spraying and absorbing tail gas by a circulating pump with the initial concentration of 100g/L, pumping absorption liquid in the absorption tower and separated ammonium hydrogen tartrate mixed slurry into a filter press for circulating filtration after the pH value of the tail gas is increased to 2.5, and finally obtaining 236kg of ammonium hydrogen tartrate crystals. Wherein the pressure filtrate is returned to the absorption tower for recycling after tartaric acid is added, and ammonium hydrogen tartrate crystals with the particle size of 1.5m are added 3 Mixing and stirring water, slowly adding ammonia water, continuing stirring for 15min after the pH value of the solution reaches 9, measuring the tartaric acid concentration of the solution to be 90.25g/L, supplementing ammonium tartrate until the tartaric acid concentration is 100g/L, adjusting the pH value to be 9.5 by using ammonia water, and adding a germanium back-extraction agent storage tank for later use.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that numerous changes and modifications can be made by those skilled in the art without departing from the inventive concepts and it is intended that such changes and modifications be covered by the present invention.

Claims (10)

1. A method for producing germanium concentrate by back extraction from hydroxamic acid loaded organic phase is characterized by comprising the following steps:
s1 back extraction: mixing and extracting alkaline ammonium tartrate aqueous solution serving as a back extraction agent and a germanium-containing hydroxamic acid loaded organic phase to obtain a germanium-containing back extraction solution and a back extracted organic phase;
s2 germanium precipitation: mixing and neutralizing the germanium-containing back extraction solution and an alkaline reagent, and performing solid-liquid separation to obtain a germanium-containing precipitate and a germanium-precipitated solution;
s3 calcination: calcining and crushing the precipitate obtained in the step S2 to obtain germanium concentrate, and absorbing calcined tail gas by an acid solution until the calcined tail gas reaches the standard and is discharged.
2. The method of claim 1, wherein the alkaline reagent in step S2 is an alkaline ammonia reagent, and the germanium-precipitated liquid obtained in step S2 is returned to step S1 to be used as a stripping agent.
3. The method of claim 1, further comprising step S4 of back extraction organic phase treatment: and (4) washing the organic phase after back extraction generated in the step S1 by using pure water, using the washed regenerated organic phase as an extracting agent, and using the washing liquid as a preparation raw material of the back extraction agent after being concentrated.
4. The method according to any one of claims 1 to 3, wherein the acidic solution in step 3 is a tartaric acid solution with a concentration of 50 to 250 g/L.
5. The method according to claim 4, further comprising a step S0 of back extractant formulation: adding an alkaline ammonia reagent into the ammonium tartrate aqueous solution to adjust the solution to be alkaline, thereby obtaining a stripping agent; wherein the concentration of the ammonium tartrate aqueous solution is 0.25-3 mol/L.
6. The method according to claim 5, wherein in step S3, the tartaric acid solution absorbs the tail gas until the pH value reaches 1-5, the solution is replaced and the precipitated precipitate is cleaned, the solution and the precipitated precipitate are subjected to solid-liquid separation to obtain an absorbed solution and a filter residue, the absorbed solution is used as a raw material of the tartaric acid solution in step S3, and the filter residue is used as a raw material for preparing the stripping agent in step S0.
7. The method according to claim 6, wherein the volume ratio of the organic phase after the back extraction to the pure water in the step S4 is 4: 1-20: 1, the number of extraction stages is 2-5, the extraction time is 2-15 minutes, and the temperature is 25-65 ℃.
8. The method of claim 7, wherein the alkaline ammonia reagent in step S0 and/or the alkaline ammonia reagent in step S2 is one of ammonia water, ammonium carbonate and liquid ammonia.
9. The method according to claim 8, wherein the pH value of the stripping agent obtained in step S0 is 7.5-9.5.
10. The method according to claim 9, wherein the volume ratio of the germanium-containing hydroxamic acid loaded organic phase to the stripping agent in step S1 is 1:1 to 15:1, the number of stripping stages is 2 to 5, the extraction time is 2 to 15 minutes, and the temperature is 25 ℃ to 65 ℃.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4568526A (en) * 1980-08-15 1986-02-04 Societe Miniere Et Metallurgique De Penarroya Process for selective liquid-liquid extraction of germanium
EP0313201A1 (en) * 1987-09-29 1989-04-26 Cominco Ltd. Recovery of germanium from aqueous solutions by solvent extraction
RU2008102352A (en) * 2008-01-21 2009-07-27 Институт химии и химической технологии СО РАН (ИХХТ СО РАН) (RU) METHOD FOR REMOVING GERMANY FROM SULFURIC ACID SOLUTIONS
CN110791648A (en) * 2019-11-07 2020-02-14 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 Method for extracting and recovering germanium from sulfuric acid leaching solution
CN110938752A (en) * 2019-11-07 2020-03-31 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 Extraction process for improving recovery rate of germanium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4568526A (en) * 1980-08-15 1986-02-04 Societe Miniere Et Metallurgique De Penarroya Process for selective liquid-liquid extraction of germanium
EP0313201A1 (en) * 1987-09-29 1989-04-26 Cominco Ltd. Recovery of germanium from aqueous solutions by solvent extraction
RU2008102352A (en) * 2008-01-21 2009-07-27 Институт химии и химической технологии СО РАН (ИХХТ СО РАН) (RU) METHOD FOR REMOVING GERMANY FROM SULFURIC ACID SOLUTIONS
CN110791648A (en) * 2019-11-07 2020-02-14 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 Method for extracting and recovering germanium from sulfuric acid leaching solution
CN110938752A (en) * 2019-11-07 2020-03-31 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 Extraction process for improving recovery rate of germanium

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