CN115109950B - 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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CN115109950B
CN115109950B CN202210662226.2A CN202210662226A CN115109950B CN 115109950 B CN115109950 B CN 115109950B CN 202210662226 A CN202210662226 A CN 202210662226A CN 115109950 B CN115109950 B CN 115109950B
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germanium
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stripping
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CN115109950A (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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Danxia Smelter Of Shenzhen Zhongjin Lingnan Nonfemet Co ltd
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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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 of the invention comprises the following steps: s1 back extraction: mixing and extracting an alkaline ammonium tartrate aqueous solution serving as a stripping agent with a germanium-containing hydroxamic acid load organic phase to obtain a germanium-containing stripping solution and a stripped organic phase; s2, germanium deposition: mixing and neutralizing the germanium-containing back extraction liquid with an alkaline reagent, and carrying out solid-liquid separation to obtain germanium-containing precipitate and germanium-precipitating liquid; s3, calcining: and (3) 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 discharge standard. The method has the advantages of low consumption of the stripping agent and difficult generation of precipitation 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 recovery of scattered germanium metal, in particular to a back extraction process for extracting germanium from a hydroxamic acid loaded organic phase.
Background
Germanium has been found in the 19 th century to be widely used in the fields of semiconductors, aerospace measurement and control, nuclear physical detection, fiber optic communication, infrared optics, solar cells, chemical catalysts, biomedical and the like due to its unique physicochemical properties. However, germanium belongs to a rare-dispersion metal, most of germanium exists in silicate and metal ores in a rare-dispersion state in crust, and the extraction and recovery of germanium are difficult due to low grade of germanium in the ores containing germanium and slag thereof. At present, the extraction and recovery methods for 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 the present stage. Currently, the extracting agents used for extracting and recovering germanium by an extraction method can be generally divided into three types, namely hydroxamic and quinoline; secondly, an amine extractant; thirdly, hydroxamic acid extractant. Among the main products of hydroxamic acid extractants commonly used at present are YW100, 7815, H106, HGS98, G315, G8315, etc. The hydroxamic acid extractant is not usually used for extracting germanium independently, other extractants are needed to be added to form a synergistic extractant system, and the extractants matched for use mainly comprise P204, N235, fatty acid and the like, and are generally used most widely by P204. And after germanium is extracted by an extraction method, germanium is back extracted from the loaded organic phase to further prepare germanium concentrate with higher purity.
The existing 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 stripping efficiency of an ammonium sulfate system is low, and the ammonium sulfate system is less used in production; the application reports of perchloric acid and hypochlorous acid are less; the back extraction effect is better by taking hydrofluoric acid and ammonium fluoride as main materials, but the germanium enrichment liquid contains fluorine, so that the problems of low safety, serious corrosion, large environmental pollution, poor product quality and the like are caused; the ammonium tartrate can avoid the problems, but the ammonium tartrate has large consumption of the stripping agent in the stripping process, is easy to generate precipitation to cause the blockage of the extraction box pipeline, can cause extraction interruption in severe cases, and needs to be cleaned regularly, thereby increasing the production cost.
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 back extraction from a hydroxamic acid loaded organic phase, which has the advantages of high safety and low back extraction agent consumption.
A method for producing germanium concentrate by back extraction from a hydroxamic acid loaded organic phase, comprising the following steps:
s1 back extraction: mixing and extracting an alkaline ammonium tartrate aqueous solution serving as a stripping agent with a germanium-containing hydroxamic acid load organic phase to obtain a germanium-containing stripping solution and a stripped organic phase;
s2, germanium deposition: mixing and neutralizing the germanium-containing back extraction liquid with an alkaline reagent, and carrying out solid-liquid separation to obtain a germanium-containing precipitate and a germanium-precipitating liquid;
s3, calcining: and (3) 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 discharge standard.
The scheme has the advantages that the consumption of the stripping agent is small in the stripping process, no sediment is generated in the stripping process, the regular cleaning is not needed, and the stripping product does not contain fluorine.
Further, the alkaline reagent in the step S2 is an alkaline ammonia reagent, and the germanium-precipitating solution obtained in the step S2 is returned to the step S1 to be used as a stripping agent. The scheme has the advantages that no ammonia gas volatilizes in the germanium precipitation process, the precipitate is easy to treat, and the obtained germanium concentrate has high germanium-containing grade.
Further, the method also comprises the step of S4 of treating the organic phase after back extraction: and (3) washing the organic phase after back extraction generated in the step (S1) by using pure water, wherein the washed regenerated organic phase is used as an extractant, and the washing liquid is concentrated and then used as a preparation raw material of the back extraction agent. Wherein the extractant is an extractant for extracting and recovering germanium by an extraction method. The scheme has the advantages that no precipitation is generated in the washing process, and the washing liquid can be recycled, so that the production cost is reduced.
Further, the acidic solution in the step S3 is 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 back-extraction agent preparation: 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, when the tartaric acid solution absorbs the tail gas until the pH 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 liquid and filter residues, the absorbed liquid is used as a raw material of the tartaric acid solution in the step S3, and the filter residues are used as a raw material for preparing the stripping agent in the step S0. The scheme has the advantages of recycling tail gas, avoiding the step of treating and absorbing dangerous waste residues in the traditional process, reducing the production cost and being more environment-friendly.
Further, the volume ratio of the organic phase to the pure water after back extraction in the step S4 is 4:1-20:1, the extraction stage number is 2-5, the extraction time is 2-15 minutes, and the temperature is 25-65 ℃.
Further, the alkaline ammonia reagent in the step S0 and/or the alkaline ammonia reagent in the 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 mixing volume ratio of the germanium-containing hydroxamic acid loaded organic phase to the stripping agent is 1:1-15:1, the number of the stripping stages is 2-5, the extraction time is 2-15 minutes, and the temperature is 25-65 ℃.
For a better understanding and implementation, the present invention is described in detail below with reference to the drawings.
Drawings
FIG. 1 is a schematic flow chart of the method for producing germanium concentrate by back extraction from hydroxamic acid loaded organic phase according to the present invention.
Detailed Description
The invention analyzes the back extraction process aiming at the problems of high back extraction agent consumption, more sediment generation and easy blockage of the extraction box pipeline in the back extraction process in the process of extracting germanium from the hydroxamic acid loaded organic phase by taking ammonium tartrate solution as the back extraction agent in the prior art.
In the conventional preparation of germanium concentrate, the chelation with hydroxamic acid in the sulfuric acid solution containing germanium realizes extraction, and the germanium and the extractant hydroxamic acid generate stable complexes, namely the hydroxamic acid loaded organic phase. In the process of back-extracting 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. Since the organic phase obtained after the extraction of germanium from the germanium-containing sulfuric acid solution by hydroxamic acid entrains a small amount of acid-containing feed liquid or acid-containing washing liquid, and the hydroxamic acid is also released during the back extraction of germanium from the hydroxamic acid-loaded organic phase by the ammonium tartrate solution, the ionization of hydrogen ions from the small amount of acid during the back extraction process can be in ion competition with excessive ammonium tartrate in the back extraction agent, namely one hydrogen ion replaces one ammonium ion in molecules, and the following side reactions occur:
(NH 4 ) 2 C 4 H 4 O 6 +H + ＝NH 4 HC 4 H 4 O 6 +NH 4 +
because the solubility (2.7 g/100g water at 20 ℃) of ammonium bitartrate generated by side reaction is obviously lower than that of ammonium bitartrate (63 g/100g water at 20 ℃), saturated ammonium bitartrate can be separated out and deposited on the bottom of a clarifying tank and an overflow weir of a mixing chamber in the process, so that a pipeline of an extraction tank is blocked, extraction flow is blocked when serious, the separated ammonium bitartrate also has no back extraction effect, the ammonium bitartrate consumption is increased, the production cost is increased, and an extraction system needs to be cleaned regularly.
For 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 which ranges from 6.0 to 7.0).
At this time, as the back extraction process is performed in an alkaline environment, acid carried in the organic phase and hydroxamic acid released after back extraction of germanium firstly undergo neutralization reaction and saponification reaction with alkali respectively to generate corresponding salt and ammonium hydroxamate, so that the ammonium tartrate is prevented from being converted into ammonium bitartrate.
Further optimally, the stripping agent can be an aqueous ammonium tartrate solution with a basic ammonia reagent to adjust the pH to basic. At this time, because of the existence of excessive alkaline ammonia reagent in the environment, if part of ammonium bitartrate is still precipitated in the back extraction process, the ammonium bitartrate is dissolved and converted into ammonium tartrate again when encountering a small amount of alkaline ammonia reagent, namely ammonium ions replace hydrogen ions, and the process is the reverse reaction of the 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 conventional ammonium tartrate aqueous solution, and particularly, the improvement of the ammonium tartrate aqueous solution which is adjusted to be alkaline by using the alkaline ammonia reagent can effectively inhibit the problem of precipitation in the ammonium tartrate stripping process, and simultaneously 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 can be one of common alkaline reagents such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate and the like, and the alkaline reagent can be subjected to neutralization reaction with the strip liquor to generate germanium-containing precipitate. However, the addition of strong alkali such as sodium hydroxide and potassium hydroxide causes volatilization of ammonia gas during germanium precipitation, thus requiring an additional waste gas treatment process, while the addition of reagent such as sodium carbonate causes difficulty in removing ammonium during subsequent calcination of germanium-containing precipitate, thus affecting the quality of germanium concentrate, so that the alkaline reagent is preferably an alkaline ammonia reagent in this step. The alkaline ammonia reagent can avoid the problems, and can make the components of the solution after germanium precipitation simpler, and can be directly returned to the back extraction step to be used as a back extraction agent, so that the consumption of the back extraction agent 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 germanium-containing precipitate after germanium precipitation. The ammonium germanium tartrate is decomposed into substances such as germanium oxide, ammonia gas, carbon dioxide and the like at high temperature in the calcination process of the germanium-containing precipitate, and the decomposed ammonia gas can be absorbed by adopting tartaric acid solution as absorption liquid to generate ammonium bitartrate in an acidic environment. The pH of the liquid obtained after absorption after the mixed liquid of the absorption tower is cleaned and the liquid is subjected to solid-liquid separation can be adjusted to be used as the absorption liquid, and the obtained ammonium bitartrate 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 stripping agent. Therefore, the tartaric acid solution is used as the tail gas absorption liquid, so that on one hand, the exhaust emission can be reduced, and on the other hand, the ammonia gas can be recovered, and the resource utilization is realized.
On the other hand, the invention changes the washing mode of the organic phase in the conventional method from dilute sulfuric acid washing to pure water washing, thereby avoiding the problem that ammonium bitartrate is separated out by the reaction of sulfuric acid and ammonium tartrate carried in the organic phase when the organic phase is washed in the conventional method, and further avoiding the problems that the composition of the washing liquid obtained after the dilute sulfuric acid washing is complex, lime neutralization treatment is needed and a large amount of dangerous waste residues are generated.
The following is a basic embodiment of the solution according to the invention, comprising the following steps:
s0, preparing a back extraction agent: adding ammonium tartrate into water, stirring and mixing until the ammonium tartrate is completely dissolved, and slowly adding an alkaline ammonia reagent in the stirring process until the solution is alkaline 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 with a germanium-containing hydroxamic acid loaded organic phase, and clarifying and separating to obtain germanium-containing stripping solution and a post-stripping organic phase;
and (3) respectively carrying out subsequent treatment on the germanium-containing stripping solution obtained in the step (S1) and the organic phase after stripping.
Wherein the treatment of the germanium-containing strip liquor comprises the following steps:
s2, germanium deposition: pumping the germanium-containing back extraction liquid into a reaction kettle, starting stirring, introducing an alkaline reagent into the bottom, fully absorbing and neutralizing, filtering by a filter press to obtain germanium-containing precipitate and germanium-precipitating back liquid, and adding the germanium-precipitating back liquid into a germanium back extraction tank for recycling. Wherein the alkaline reagent is preferably alkaline ammonia reagent, and further preferably one of ammonia water, ammonium carbonate and liquid ammonia.
S3, calcining: and (3) adding the germanium-containing precipitate obtained in the step (S2) into a calciner for calcination, and absorbing tail gas by using tartaric acid solution in the calcination process. Crushing and packing the calcined solid to obtain germanium concentrate. The filtrate obtained after absorbing the tail gas and the precipitate separated out after solid-liquid separation is used as the raw material of the tartaric acid solution in the step S4, and the filter residue is used as the raw material for preparing the stripping agent in the step S1. The treatment of the organic phase after stripping comprises the following steps:
and S4, organic phase treatment after back extraction: and (3) mixing and washing the organic phase obtained in the step (S1) after 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 used as an organic extractant of germanium for recycling.
S5, washing liquid treatment: and (3) evaporating and concentrating the washing liquid, analyzing the content of tartaric acid, adding tartaric acid and 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 up against the stripping process in step S1 using a conventional tartaric acid solution and a basic ammonium tartrate solution as stripping agents; examples 2 and 3 are set for the selection of different parameters in each step in the basic embodiment; examples 4 and 5 were set for the reuse methods of the filtrate and the filter residue in step S3, respectively.
Example 1
200mL of 2mol/L ammonium tartrate solution was prepared for use.
100mL of germanium-loaded organic phase consisting of 5% P204+2% YW100+93% solvent oil is added into a 250mL beaker, and mixed with 100mL of prepared 2mol/L ammonium tartrate solution according to the volume of 1:1 for 15min. The organic phase and the bottom of the beaker were separated to form a white precipitate, the organic phase was separated by a separating funnel, and the remaining solution and the precipitate were suction-filtered under negative pressure to obtain 17.06g of precipitate.
And adding ammonia water into the rest prepared 2mol/L ammonium tartrate solution to adjust the pH value to 9.0, measuring 100mL by using a measuring cylinder, 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. After back extraction, the phase separation is good, and no sediment is generated in the organic phase and the back extraction liquid.
Example 2
An embodiment for back extraction production of germanium concentrate from hydroxamic acid loaded organic phase, comprising the steps of:
s0, preparing a back extraction agent: adding 500kg of ammonium tartrate into 1m3 of aqueous solution, stirring and mixing until the ammonium tartrate is completely dissolved, and slowly adding ammonia water into the solution until the pH value is 9 in the stirring process to obtain the stripping agent.
S1 back extraction: 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, wherein the mixing time is 5min, carrying out stripping for 4 stages, the temperature is 45 ℃, and clarifying and separating to obtain germanium-containing stripping liquid of a water phase and an organic phase after stripping. The pH of the strip solution was found to be 7.8, with 6.4g/L germanium. Wherein the hydroxamic acid loaded organic phase has a composition of 10% p204+5% yw100+85% mineral spirits.
And (3) respectively carrying out subsequent treatment on the germanium-containing stripping solution obtained in the step (S1) and the organic phase after stripping, wherein the treatment on the germanium-containing stripping solution is as follows:
s2, germanium deposition: pumping the germanium-containing back extraction liquid into a reaction kettle, starting stirring, introducing liquid ammonia into the bottom, fully absorbing and neutralizing to pH value of 8.8, continuing to react for 1 hour, and filtering by a filter press to obtain 28kg of wet precipitate and germanium-precipitating back liquid. At the moment, analyzing to obtain the grade 41% of germanium in the solid which contains 55% of moisture in the wet precipitate and no moisture; the germanium content in the germanium-precipitating liquid is 1.2g/L, the tartaric acid content is 71.7g/L, and the germanium-precipitating liquid is added into a germanium back-extraction agent tank for recycling.
S3, calcining: and (3) adding the wet precipitate obtained in the step (S2) into a baffle plate calciner, setting the temperature to 450 ℃, calcining for 4 hours, and absorbing tail gas by adopting a tartaric acid solution with the concentration of 50g/L in the calcining process. Crushing and packing the calcined solid to obtain 9.9kg of germanium concentrate, and analyzing to obtain 51.2% of germanium contained in the germanium concentrate; after tail gas absorption, the absorption liquid can be added into a germanium back-extraction agent tank for recycling after treatment.
The organic phase after back extraction is treated as follows:
and S4, organic phase treatment after back extraction: mixing the organic phase obtained in the step S1 after back extraction with pure water according to the volume ratio of 4:1, washing for 5min at 45 ℃ through 2 stages, and clarifying and separating to obtain washing liquid of a water phase and a regenerated organic phase. At this time, the concentration of tartaric acid in the washing liquid was found to be 3.9g/L. The regenerated organic phase can be used as an organic extractant of germanium for recycling.
S5, washing liquid treatment: the washing solution is evaporated and concentrated for 13 times, the tartaric acid content after analysis and concentration is 48.7g/L, the tartaric acid is added to 89.7g/L, ammonia water is added to adjust the pH value to 8.2, and then the solution is added into a germanium stripping agent tank for recycling. The condensed water evaporated in this process is added to the pure water in step S4 for washing the organic phase.
According to the method for producing germanium concentrate, the germanium recovery rate reaches 97.5% from the loaded germanium organic phase to the germanium concentrate.
Example 3
This example is another embodiment of the invention for back-extraction of germanium concentrate from hydroxamic acid loaded organic phase comprising the steps of:
s0, preparing a back extraction agent: 2500kg of ammonium tartrate is added into 5m3 of water solution, stirred and mixed until the ammonium tartrate is completely dissolved, and ammonia water is slowly added into the solution until the pH value is 8.8 in the stirring process, so as to obtain the stripping agent.
S1 back extraction: mixing the stripping agent obtained in S0 with the germanium-loaded organic phase according to the volume ratio of 1:15, wherein the mixing time is 5min, carrying out stripping 2 stages, and clarifying and separating at the temperature of 35 ℃ to obtain germanium-containing stripping liquid and a stripping organic phase. At this time, the back extraction liquid contains 5.4g/L germanium. Wherein the hydroxamic acid loaded organic phase has a composition of 10% p204+5% yw100+85% mineral spirits.
And (3) respectively carrying out subsequent treatment on the germanium-containing stripping solution obtained in the step (S1) and the organic phase after stripping, wherein the treatment on the germanium-containing stripping solution is as follows:
s2, germanium deposition: pumping the germanium-containing back extraction liquid into a reaction kettle, starting stirring, introducing liquid ammonia into the bottom, fully absorbing and neutralizing to a pH value of 8.9, reacting for 2 hours, and filtering the solution by a filter press to obtain 140kg of wet precipitate and germanium-precipitating back liquid. At the moment, analyzing to obtain the grade of 40% of germanium in solids which contain 60% of moisture in the wet precipitate; the germanium content in the germanium-precipitating liquid is 0.8g/L, the tartaric acid content is 33.5g/L, and the germanium-precipitating liquid is added into a germanium back-extraction agent tank for recycling.
S3, calcining: and (3) adding the wet precipitate obtained in the step (S2) into a baffle plate calciner, setting the temperature to 500 ℃, calcining for 4 hours, and absorbing tail gas by adopting a tartaric acid solution with the concentration of 50g/L in the calcining process. Crushing and packing the calcined solid to obtain germanium concentrate, and analyzing 45.3kg of germanium concentrate with 49.2% of germanium in the germanium concentrate; the absorption liquid after absorbing the tail gas can be added into a germanium back-extraction agent tank for recycling after being treated.
The organic phase after back extraction is treated as follows:
and S4, organic phase treatment after back extraction: and (3) washing the organic phase obtained in the step (S1) by 5 stages of pure water, wherein the mixing time is 5min, the volume ratio of the organic phase to the pure water is 4:1, and the temperature is 35 ℃. The washing liquid and the regenerated organic phase are obtained after clarification and separation. At this time, the concentration of tartaric acid in the washing solution was found to be 4.6g/L. The regenerated organic phase can be used as an organic extractant of germanium for recycling.
S5, washing liquid treatment: after the washing liquid is evaporated and concentrated for 12 times, the tartaric acid content is detected to be 51.5g/L, and the tartaric acid content is added into a germanium stripping agent tank for recycling. The condensed water evaporated in this process is added to the pure water in step S4 for washing the organic phase.
According to the method for producing germanium concentrate described above, the germanium recovery rate was 96.9% from the germanium loaded organic phase to the germanium concentrate.
Example 4
This example is a method of carrying out the invention of step S4 using the absorbed solution and the separated precipitate as raw materials for stripping agent, wherein the volume of tartaric acid solution for absorbing tail gas is 1.5m 3 And when the initial concentration is 50g/L, the tail gas is absorbed by spraying through a circulating pump, and the pH value of the absorption liquid to be detected is 1.5, pumping the mixed slurry of the absorption liquid in the absorption tower and the separated ammonium bitartrate into a filter press for circulating filtration, and finally obtaining 128kg of ammonium bitartrate crystals. Wherein the filter pressing liquid is returned to the absorption tower for recycling after the tartaric acid is added, and the ammonium bitartrate is crystallized and is 1.5m 3 Mixing water, stirring, slowly adding ammonia water, stirring for 15min after pH value of the solution reaches 9, and measuringThe concentration of tartaric acid is 44g/L, ammonium tartrate is added to the concentration of tartaric acid of 100g/L, ammonia water is used for adjusting the pH value to 9.5, and then the mixture is added into a germanium back extraction agent storage tank for standby.
Example 5
This example is another implementation method of the step S4 of the present invention using the absorbed solution and the separated precipitate as raw materials of the stripping agent, wherein the volume of the tartaric acid solution for absorbing tail gas is 1.5m 3 And (3) spraying and absorbing tail gas with the initial concentration of 100g/L by a circulating pump, pumping the mixed slurry of the absorption liquid in the absorption tower and the separated ammonium bitartrate into a filter press for circulating filtration after the pH value of the tail gas is raised to 2.5, and finally obtaining 236kg of ammonium bitartrate crystals. Wherein the filter pressing liquid is returned to the absorption tower for recycling after the tartaric acid is added, and the ammonium bitartrate is added with 1.5m by crystallization 3 Mixing and stirring water, slowly adding ammonia water, continuously 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, adding ammonium tartrate to the tartaric acid concentration of 100g/L, adjusting the pH value to be 9.5 by using the ammonia water, and adding the germanium back-extraction agent into a storage tank for standby.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and the invention is intended to encompass such modifications and improvements.

Claims (10)

1. A method for producing germanium concentrate by back extraction from a hydroxamic acid loaded organic phase, comprising the steps of:
s0, preparing a back-extraction agent: adding an alkaline ammonia reagent into the ammonium tartrate aqueous solution to adjust the solution to be alkaline, thereby obtaining a stripping agent;
s1 back extraction: mixing and extracting an alkaline ammonium tartrate aqueous solution serving as a stripping agent with a germanium-containing hydroxamic acid load organic phase to obtain a germanium-containing stripping solution and a stripped organic phase;
s2, germanium deposition: mixing and neutralizing the germanium-containing back extraction liquid with an alkaline ammonia reagent, and carrying out solid-liquid separation to obtain germanium-containing precipitate and germanium-precipitating liquid;
s3, calcining: and (3) 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 discharge standard.
2. The method according to claim 1, wherein the germanium-precipitated liquid obtained in step S2 is returned to step S1 for use as a stripping agent.
3. The method according to claim 1, further comprising the step of S4 post-stripping organic phase treatment: and (3) washing the organic phase after back extraction generated in the step (S1) by using pure water, wherein the washed regenerated organic phase is used as an extractant, and the washing liquid is concentrated and then used as a preparation raw material of the back extraction agent.
4. A process according to any one of claims 1 to 3, wherein the acidic solution in step S3 is a tartaric acid solution having a concentration of 50 to 250g/L.
5. The method according to claim 4, wherein the concentration of the aqueous solution of ammonium tartrate is 0.25 to 3mol/L.
6. The method according to claim 5, wherein in the step S3, the tartaric acid solution is changed to a solution when the pH value reaches 1 to 5, and the precipitated precipitate is cleaned, and the solution and the precipitated precipitate are subjected to solid-liquid separation to obtain an absorbed liquid and a filter residue, wherein the absorbed liquid 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.
7. The method according to claim 6, wherein 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 extraction stage number is 2-5, the extraction time is 2-15 minutes, and the temperature is 25-65 ℃.
8. The method according to 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 of the stripping agent obtained in the step S0 is 7.5-9.5.
10. The method according to claim 9, wherein the mixing volume ratio of the germanium-containing hydroxamic acid loaded organic phase to the stripping agent in the step S1 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 ℃.
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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

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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