CN113789445A - Method for regenerating ineffective gallium and germanium extractant by organic phase separation - Google Patents
Method for regenerating ineffective gallium and germanium extractant by organic phase separation Download PDFInfo
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Abstract
The invention discloses a method for regenerating an ineffective gallium and germanium extractant by organic phase separation. According to the invention, the degraded extractant is used for purifying and separating components, and the acid phosphate type extractant and the alkyl hydroximic acid compounded extractant are subjected to acid back-extraction to obtain organic phase accumulated metal ions so as to eliminate the influence of the metal ions on the subsequent oximation reaction; separating the diluent and the acidic phosphate type extracting agent in the organic phase part, wherein the separated diluent and the acidic phosphate type extracting agent can be recycled, and the recovery rate is more than 95%; the fatty acid obtained by separation is used as a raw material for synthesizing alkyl hydroximic acid to carry out product synthesis, and the effective component is more than 80 percent after synthesis. The hydroximic acid regeneration method provided by the invention recycles the waste extracting agent, so that on one hand, the consumption of purchasing cost is reduced, and on the other hand, the environmental pollution and resource waste caused by treatment of the waste extracting agent are avoided.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of waste extracting agents, and particularly relates to a method for regenerating an ineffective gallium and germanium extracting agent by organic phase separation.
Background
The extractant compounded by the acid phosphate type extractant and the hydroximic acid is an extractant for efficiently extracting gallium and germanium in a sulfuric acid system, wherein the hydroximic acid is a functional group organic reagent with efficient chelating performance, related products comprise alkyl hydroximic acid, octyl hydroximic acid, acetyl hydroximic acid and the like, the alkyl hydroximic acid is an efficient beneficiation reagent and has efficient gallium and germanium extraction performance, a synergistic extraction system is usually compounded with the acid phosphate type extractant, the dosage of the reagent can be reduced on one hand, the synergistic extraction system has better extraction effect than an alkyl hydroximic acid independent system on the other hand, after the compounded extractant is subjected to multi-stage extraction, the gallium and germanium extraction rate can respectively reach more than 99 percent, high-acid back extraction of gallium and fluoride back extraction of germanium are generally adopted, and the alkyl hydroximic acid has higher water solubility and hydrolyzability in the use process, to ensure the extraction effect, the alkyl hydroximic acid is generally continuously added into the organic phase.
Hydroximic acids are derivatives of carboxylic acids, which are less acidic than the corresponding carboxylic acids. In acidic solutions, hydroxamic acids are readily hydrolyzed to hydroxylamine and carboxylic acids.
RCONHOH+H2O→RCOOH+NH2OH
Degradation product NH2OH is dissolved in a water phase in an extraction system, RCOOH is used as a basic raw material for synthesizing hydroximic acid and always exists in an organic phase, the concentration of RCOOH is higher and higher along with long-term accumulation, on one hand, the balance of extraction volume is damaged, so that the extraction volume expands, some organic phases need to be discharged periodically to maintain the extraction system, the loss of an extractant is caused, the operation cost is increased, and the discharged ineffective waste extractant is generally combusted by a pyrogenic process, so that the environmental pollution or outsourcing treatment is caused; on the other hand, the extraction rate of germanium is influenced, and the production is difficult.
No matter the alkyl hydroximic acid synergistic extraction system or the alkyl hydroximic acid extraction system, the extraction effect can be ensured by continuously supplementing the alkyl hydroximic acid in the operation process, the alkyl hydroximic acid is generally synthesized by taking C5-C9 fatty acid as a raw material, and the effective content of the hydroximic acid is generally more than 60 percent after synthesis. It has been found that, in addition to the problem of high water solubility, alkyl hydroxamic acids exhibit instability in high acid extracts, which can decompose to fatty acids and hydroxylamines upon prolonged contact or mixing with high acid extracts.
Therefore, the extraction organic phase of the long-term running extraction organic system, which is mainly composed of alkyl hydroximic acid, acidic phosphate ester type extracting agent and diluent, is gradually changed into the extraction system of fatty acid, acidic phosphate ester type extracting agent and diluent, so that the extraction system is broken down in the past and finally loses the extraction capacity.
On the other hand, the continuous supplement of the alkyl hydroximic acid has very high cost, is an important expense in production and seriously influences the economic benefit.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a method for regenerating the ineffective gallium and germanium extractant by organic phase separation.
In order to realize the technical purpose, the invention provides a method for regenerating a failed gallium and germanium extractant by organic phase separation, which comprises the following steps:
s1: adding dilute acid into the degraded waste extracting agent, mixing and then putting into oscillation equipment for reaction; wherein the extractant is formed by compounding an acidic phosphate type extractant and hydroximic acid;
s2: after the reaction is finished, separating an organic phase from a water phase by using liquid separation equipment, washing the organic phase with water until the pH value of the organic phase is 6-7;
s3: adding the washed organic phase into an alkaline solution, stirring and reacting for a certain time at normal temperature, standing, and separating the lower alkaline sodium aliphatate solution by using a liquid separation device to obtain an extracted organic phase, wherein the extracted organic phase is a diluent of an extraction system and saponified acidic phosphate, and the extracted organic phase is collected and regenerated by adding acid and can be reused; adding acid into the lower alkaline sodium fatty acid solution for neutralization, converting the sodium fatty acid into fatty acid, separating liquid, and taking the separated fatty acid organic phase as a subsequent synthesis raw material;
s4: adding the fatty acid obtained in the step S3 into a reaction kettle, adding acid and alcohol, carrying out heating reflux reaction for a period of time, cooling and standing, then separating a lower-layer acid solution by using a liquid separation device, washing an organic phase with water, and washing with water until the pH value is 6-7 to obtain fatty acid ester; wherein the acid acts as a catalyst;
s5: adding fatty acid ester, hydroxylamine salt and water into a reaction bottle, stirring and dissolving, slowly dripping alkali liquor for reaction, dripping dilute acid until the pH value of the solution is 4-5 after the reaction is finished, and standing and separating to obtain regenerated hydroximic acid.
Further, the volume ratio of the degraded waste compound extractant to the dilute acid in the step S1 is 1: 0.2-2, and the reaction time is 0.5-2 hours.
Further, the diluted acid in the step S1 is one or a combination of a sulfuric acid solution of 200-300 g/L, a hydrochloric acid solution of 150-300 g/L, and an oxalic acid solution of 50-150 g/L.
Further, the alkaline solution in the step S3 is an alkaline solution prepared by sodium hydroxide and having a concentration of 50-300 g/L; the reaction time is 1-4 hours, and the standing time is 4-12 hours.
Further, when the reflux reaction is performed in the step S4, the fatty acid: alcohol: acid catalyst ═ 1: 0.2-0.8: 0.2 to 0.4; the reflux reaction temperature is 80-84 ℃, and the reflux reaction time is 4-10 hours.
Further, the alcohol in the step S4 is a lower alcohol of C1-C3, preferably methanol; the acid catalyst is one of 98% concentrated sulfuric acid and 85% concentrated phosphoric acid, preferably 98% concentrated sulfuric acid.
Further, in the step S5, the ratio of fatty acid ester: hydroxylamine salts: base 1: (1.0-3): (1.5-3), preferably fatty acid ester: hydroxylamine salts: base 1: (1.0-2): (2-3).
Further, the alkali solution in the step S5 is prepared from alkali and water, and the mass of the water is 0.8 to 2 times of the mass of the fatty acid ester.
Further, the reaction process in the step S5 includes the specific steps of controlling the temperature of the reaction system to be lower than 30 ℃, slowly adding the alkali solution into the mixed system composed of the fatty acid ester and the hydroxylamine salt aqueous solution in the step S4, reacting for 2-6 hours, raising the temperature to 40-65 ℃, and reacting for 2-6 hours.
Further, the alkali in step S5 is one of sodium hydroxide or potassium hydroxide.
Compared with the prior art, the method has the advantages that the degraded extractant is subjected to purification component separation, metal ions in the extractant are back-extracted to eliminate the influence of the metal ions on the oximation reaction, the metal ions are partially separated out as the acidic phosphate type extractant and the diluent, the separated acidic phosphate type extractant and the separated diluent can be recycled through acidification regeneration, and the recovery rate is over 95 percent; the fatty acid obtained by separation is used as a raw material for synthesizing alkyl hydroximic acid to carry out product synthesis, and the effective component is more than 80 percent after synthesis. The gallium and germanium extractant regeneration method provided by the invention reuses the waste extractants, so that on one hand, the consumption of purchasing cost is reduced, and on the other hand, the environmental pollution and resource waste caused by processing the waste extractants are avoided.
Detailed Description
The following examples are provided to facilitate understanding of the present invention, but are not intended to limit the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
A method for regenerating a failed gallium and germanium extractant by organic phase separation comprises the following steps,
s1: adding dilute acid into the degraded waste extracting agent, mixing and then putting into oscillation equipment for reaction; wherein the extractant is formed by compounding an acidic phosphate type extractant and hydroximic acid;
the step is mainly to realize back extraction purification of the metal ions possibly remaining in the extracting agent under the condition of high acid so as to eliminate the influence of the metal ions on the oximation reaction.
The reaction chemical formula is:
(wherein HA represents an extractant, M represents a metal ion)
S2: after the reaction is finished, separating an organic phase from a water phase by using liquid separation equipment, washing the organic phase with water until the pH value of the organic phase is 6-7;
the aim of the step is to wash off the residual diluted acid in the reaction in the step 1 to obtain relatively pure fatty acid and acidic phosphate type extractant and diluent substance;
s3: and adding the washed organic phase into the alkaline solution, stirring and reacting for a certain time at normal temperature, standing, and separating the lower alkaline sodium aliphatate solution by using a liquid separation device to obtain an extracted organic phase. The extracted organic phase is a diluent of an extraction system, and can be recycled after being collected and regenerated by acidification; adding acid into the lower alkaline sodium fatty acid solution for neutralization, converting the sodium fatty acid into fatty acid, separating liquid, and taking the separated fatty acid organic phase as a subsequent synthesis raw material;
the main reaction of organic phase and alkali saponification in this step is:
the organic phase takes saponification reaction with 5% -30% acid phosphate ester extractant and alkali, the chemical reaction formula is: RH + NaOH → RNA + H2O (RH is an acidic phosphate type extracting agent), and the organic phase after complete saponification and the solvent oil can be dissolved in the organic phase;
fatty acid and alkali generate sodium fatty acid, and the chemical reaction formula is as follows: RCOOH + NaOH → RCOONa + H2O, wherein the fatty acid sodium is dissolved in water, and is layered with the saponified acidic phosphate extractant and the solvent oil;
the chemical reaction formula of the organic phase added diluted acid washing process in the step is as follows: RCOONa + H2SO4→RCOOH+Na2SO4(ii) a Fatty acid is separated out by liquid separation;
s4: adding the fatty acid obtained in the step S3 into a reaction kettle, adding acid and alcohol, carrying out heating reflux reaction for a period of time, cooling and standing, then separating a lower-layer acid solution by using a liquid separation device, washing an organic phase with water, and washing with water until the pH value is 6-7 to obtain fatty acid ester; wherein the acid acts as a catalyst;
s5: adding fatty acid ester, hydroxylamine salt and water into a reaction bottle, stirring to dissolve, slowly dripping alkali liquor to react, dripping diluted acid until the pH value of the solution is 4-5 after the reaction is finished, and standing and separating to obtain regenerated hydroximic acid.
The effective component of the hydroximic acid obtained by the synthesis method is not less than 80 percent, and the recycling utilization rate is more than 85 percent.
Further, the volume ratio of the degraded waste compound extractant to the dilute acid in the step S1 is 1: 0.2-2, and the reaction time is 0.5-2 hours.
Further, the diluted acid in the step S1 is one or a combination of a sulfuric acid solution of 200-300 g/L, a hydrochloric acid solution of 150-300 g/L, and an oxalic acid solution of 50-150 g/L.
Further, the alkaline solution in the step S3 is an alkaline solution prepared by sodium hydroxide and having a concentration of 50-300 g/L; the reaction time is 1-4 hours, and the standing time is 4-12 hours.
Further, when the reflux reaction is performed in the step S4, the organic phase: alcohol: acid 1: 0.2-0.8: 0.2 to 0.4; the reflux reaction temperature is 80-84 ℃, and the reflux reaction time is 4-10 hours.
Further, the alcohol in the step S4 is a lower alcohol of C1-C3, preferably methanol; the acid is one of 98% concentrated sulfuric acid and 85% concentrated phosphoric acid, preferably 98% concentrated sulfuric acid.
Further, in the step S5, the ratio of fatty acid ester: hydroxylamine salts: base 1: (1.0-3): (1.5-3), preferably fatty acid ester: hydroxylamine salts: base 1: (1.0-2): (2-3).
Further, the alkali solution in the step S5 is prepared from alkali and water, the mass of the water is 0.8-2 times of that of the fatty acid ester, and the alkali is one of sodium hydroxide and potassium hydroxide.
Further, the reaction process in the step S5 includes the specific steps of controlling the temperature of the reaction system to be lower than 30 ℃, slowly adding the alkali solution into the mixed system composed of the fatty acid ester and the hydroxylamine salt aqueous solution in the step S4, reacting for 2-6 hours, raising the temperature to 40-65 ℃, and reacting for 2-6 hours.
Example 1
S1, putting 200ml of degradation invalidation extracting agent into a 500ml closed bottle, adding 200ml of 300g/L dilute sulfuric acid, putting into an oscillator, and reacting for 0.5 hour;
s2, after the reaction is finished, adding 200ml of clear water into the organic phase, uniformly oscillating, separating the organic phase from the water phase by using a separating funnel, repeatedly mixing, oscillating and washing for 5 times, and measuring the pH value of the washing water for the last time to be 6 to obtain 190ml of the organic phase;
s3, adding 190ml of organic phase into 200ml of 100g/L sodium hydroxide solution, stirring and reacting for 60 minutes at normal temperature, standing for 6 hours, observing obvious layering phenomenon, wherein the upper layer is light yellow diluent and saponified P204, weighing a measuring cylinder to obtain 115ml, separating and acidifying, and regenerating for secondary use, wherein the recovery rate is 95.8% by using a phosphate extractant; the lower layer is brown yellow sodium aliphatate water solution, which is washed for 2 times by 20g/L dilute sulphuric acid and then washed by clean water to obtain 85ml fatty acid organic phase used for the next step;
s4, putting 85ml of fatty acid organic phase (weighing 79g), 32g of methanol and 13g of concentrated sulfuric acid into a three-neck flask, heating the oil bath to 105 ℃, keeping the internal temperature at 80-84 ℃, performing reflux reaction for 4 hours, standing, separating a lower-layer acid solution by using a separating funnel to obtain a fatty acid methyl ester organic phase, washing with clear water for multiple times, and then obtaining 96ml of fatty acid methyl ester organic phase, wherein the pH value of the washed clear water is 6-7, and weighing 85g of the fatty acid methyl ester organic phase;
s5, adding 85g of fatty acid methyl ester, 49.3g of hydroxylamine hydrochloride and 100ml of water into a reaction bottle, stirring, slowly dropwise adding 165g of sodium hydroxide alkali liquor (the content is 30%) at 28-30 ℃, reacting for 4 hours after dropwise adding is finished, and then heating to 45 ℃ for reacting for 4 hours; after the reaction is finished, the temperature is reduced to 30 ℃, 200g/L dilute sulfuric acid is dripped until the pH value of the solution is 4-5, and 84g of regenerated hydroximic acid is obtained by standing and separating.
Measuring the content of the synthesized hydroximic acid by a spectrophotometric method, adding an iron trichloride aqueous solution into the synthesized hydroximic acid, and calculating to obtain the hydroximic acid with the effective content of 81.3 percent after measuring the light absorption value.
Example 2
S1, putting 200ml of degradation invalidation extracting agent into a 500ml closed bottle, adding 200ml of 180g/L diluted hydrochloric acid, putting into an oscillator, and reacting for 0.5 hour;
s2, after the reaction is finished, adding 200ml of clear water into the organic phase, uniformly oscillating, separating the organic phase from the water phase by using a separating funnel, repeatedly mixing, oscillating and washing for 5 times, and measuring the pH value of the washing water for the last time to be 6 to obtain 188ml of the organic phase;
s3, adding 188ml of organic phase into 200ml of 150g/L sodium hydroxide solution, stirring and reacting for 90 minutes at normal temperature, standing for 6 hours, observing obvious layering phenomenon, wherein the upper layer is light yellow diluent and saponified P204, weighing 114ml of measuring cylinder, separating and acidifying, and regenerating for secondary use, wherein the recovery rate is 95.5% by using phosphate extractant; the lower layer is brown yellow sodium aliphatate water solution, which is washed for 2 times by 20g/L dilute sulphuric acid and then washed by clean water to obtain 83ml fatty acid organic phase used for the next step;
s4, putting 83ml of a fatty acid organic phase (weighing 77g), 31g of methanol and 13g of concentrated sulfuric acid into a three-neck flask, heating the three-neck flask in an oil bath to 105 ℃, keeping the internal temperature at 80-84 ℃, carrying out reflux reaction for 4 hours, standing, separating a lower-layer acid solution by using a separating funnel to obtain a fatty acid methyl ester organic phase, washing with clear water for multiple times, and then obtaining 93.6ml of the fatty acid methyl ester organic phase, weighing 83g, wherein the pH value is 6-7;
s5, adding 83g of fatty acid methyl ester, 48.2g of hydroxylamine hydrochloride and 100ml of water into a reaction bottle, stirring, slowly dropwise adding 161g of sodium hydroxide alkali liquor (the content is 30%) at 28-30 ℃, reacting for 4 hours after dropwise adding is finished, and then heating to 45 ℃ for reacting for 4 hours; after the reaction is finished, the temperature is reduced to 30 ℃, 200g/L dilute sulfuric acid is dripped until the pH value of the solution is 4-5, and 82.8 g of regenerated hydroximic acid is obtained by standing and separating.
Measuring the content of the synthesized hydroximic acid by a spectrophotometric method, adding an iron trichloride aqueous solution into the synthesized hydroximic acid, and calculating to obtain the effective content of the hydroximic acid of 82.6 percent after measuring a light absorption value.
Example 3
S1, putting 200ml of degradation invalidation extracting agent into a 500ml closed bottle, adding 100ml of 100g/L oxalic acid solution, putting into an oscillator, and reacting for 1 hour;
s2, after the reaction is finished, adding 200ml of clear water into the organic phase, uniformly oscillating, separating the organic phase from the water phase by using a separating funnel, repeatedly mixing, oscillating and washing for 5 times, and measuring the pH value of the washing water for the last time to be 6 to obtain 184ml of the organic phase;
s3, adding 184ml of organic phase into 200ml of 160g/L sodium hydroxide solution, stirring and reacting for 60 minutes at normal temperature, standing for 6 hours to observe obvious layering phenomenon, wherein the upper layer is light yellow diluent and saponified P204, a measuring cylinder is weighed to obtain 113ml, and the obtained product is regenerated after separation and acidification and is used for secondary use, and the recovery rate is 95.0% in terms of phosphate extractant; the lower layer is brown yellow sodium aliphatate water solution, which is washed for 2 times by 20g/L dilute sulphuric acid and then washed by clean water to obtain 82ml fatty acid organic phase used for the next step;
s4, placing 82ml of fatty acid organic phase (weighing 76g), 32g of methanol and 13g of concentrated sulfuric acid into a three-neck flask, heating the oil bath to 105 ℃, keeping the internal temperature at 80-84 ℃, performing reflux reaction for 4 hours, standing, separating a lower-layer acid solution by using a separating funnel to obtain a fatty acid methyl ester organic phase, washing with clear water for multiple times, and obtaining 93ml of fatty acid methyl ester organic phase, wherein the pH value of the washed clear water is 6-7, and the weight of the fatty acid methyl ester organic phase is 82.5 g;
s5, adding 82.5g of fatty acid methyl ester, 48g of hydroxylamine hydrochloride and 100ml of water into a reaction bottle, stirring, slowly dropwise adding 160g of sodium hydroxide alkali liquor (the content is 30%) at 28-30 ℃, reacting for 4 hours after dropwise adding is finished, and then heating to 45 ℃ for reacting for 4 hours; after the reaction is finished, the temperature is reduced to 30 ℃, 200g/L dilute sulfuric acid is dripped until the pH value of the solution is 4-5, and 82 g of regenerated hydroximic acid is obtained by standing and separating.
Measuring the content of the synthesized hydroximic acid by a spectrophotometric method, adding an iron trichloride aqueous solution into the synthesized hydroximic acid, and calculating to obtain the hydroximic acid with the effective content of 81.9 percent after measuring the light absorption value.
Example 4
S1, putting 200ml of degradation invalidation extracting agent into a 500ml closed bottle, adding a mixed solution of 50ml of 150g/L dilute sulfuric acid, 100ml of 150g/L dilute hydrochloric acid and 50ml of 100g/L oxalic acid, putting into an oscillator, and reacting for 0.5 hour;
s2, after the reaction is finished, adding 200ml of clear water into the organic phase, uniformly oscillating, separating the organic phase from the water phase by using a separating funnel, repeatedly mixing, oscillating and washing for 5 times, and measuring the pH value of the washing water for the last time to be 6 to obtain 187ml of organic phase;
s3, adding 190ml of organic phase into 200ml of 180g/L sodium hydroxide solution, stirring and reacting for 120 minutes at normal temperature, standing for 6 hours, observing obvious layering phenomenon, wherein the upper layer is light yellow diluent and saponified P204, weighing 114ml of measuring cylinder, separating and acidifying, and regenerating for secondary use, wherein the recovery rate is 95.2% in terms of phosphate extractant; the lower layer is brown yellow sodium aliphatate water solution, which is washed for 2 times by 20g/L dilute sulphuric acid and then washed by clean water to obtain 83.7ml fatty acid organic phase used for the next step;
s4, putting 83.7ml of fatty acid organic phase (weighing 78g), 32g of methanol and 13g of concentrated sulfuric acid into a three-neck flask, heating the oil bath to 105 ℃, keeping the internal temperature at 80-84 ℃, carrying out reflux reaction for 4 hours, standing, separating a lower-layer acid solution by using a separating funnel to obtain a fatty acid methyl ester organic phase, washing with clear water for multiple times, and then obtaining 94.8ml of fatty acid methyl ester organic phase, weighing 84g of the fatty acid methyl ester organic phase, wherein the pH value is 6-7;
s5, adding 84g of fatty acid methyl ester, 49.3g of hydroxylamine hydrochloride and 100ml of water into a reaction bottle, stirring, slowly dropwise adding 163g of sodium hydroxide alkali liquor (the content is 30%) at 28-30 ℃, reacting for 4 hours after dropwise adding is finished, and then heating to 45 ℃ for reacting for 4 hours; after the reaction is finished, the temperature is reduced to 30 ℃, 200g/L dilute sulfuric acid is dripped until the pH value of the solution is 4-5, and 84g of regenerated hydroximic acid is obtained by standing and separating.
Measuring the content of the synthesized hydroximic acid by a spectrophotometric method, adding an iron trichloride aqueous solution into the synthesized hydroximic acid, and calculating to obtain the hydroximic acid with the effective content of 81.8 percent after measuring the light absorption value.
Compared with the prior art, the invention carries out purification component separation on the degraded extractant, separates the acidic phosphate type extractant and the diluent, and can recycle the separated acidic phosphate type extractant and the diluent, and the recovery rate is more than 95%; the fatty acid obtained by separation is used as a raw material for synthesizing alkyl hydroximic acid to carry out product synthesis, and the effective component is more than 80 percent after synthesis. The hydroximic acid regeneration method provided by the invention recycles the waste extracting agent, so that on one hand, the consumption of purchasing cost is reduced, and on the other hand, the environmental pollution and resource waste caused by treatment of the waste extracting agent are avoided.
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, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A method for regenerating an ineffective gallium and germanium extractant by organic phase separation is characterized in that: comprises the following steps of (a) carrying out,
s1: adding dilute acid into the degraded waste extracting agent, mixing and then putting into oscillation equipment for reaction; wherein the extractant is formed by compounding an acidic phosphate type extractant and hydroximic acid;
s2: after the reaction is finished, separating an organic phase from a water phase by using liquid separation equipment, washing the organic phase with water until the pH value of the organic phase is 6-7;
s3: adding the washed organic phase into an alkaline solution, stirring and reacting for a certain time at normal temperature, standing, and separating the lower alkaline sodium aliphatate solution by using a liquid separation device to obtain an extracted organic phase, wherein the extracted organic phase is a diluent of an extraction system and saponified acidic phosphate, and the extracted organic phase is collected and regenerated by adding acid and can be reused; adding acid into the lower alkaline sodium fatty acid solution for neutralization, converting the sodium fatty acid into fatty acid, separating liquid, and taking the separated fatty acid organic phase as a subsequent synthesis raw material;
s4: adding the fatty acid obtained in the step S3 into a reaction kettle, adding acid and alcohol, carrying out heating reflux reaction for a period of time, cooling and standing, then separating a lower-layer acid solution by using a liquid separation device, washing an organic phase with water, and washing with water until the pH value is 6-7 to obtain fatty acid ester; wherein the acid acts as a catalyst;
s5: adding fatty acid ester, hydroxylamine salt and water into a reaction bottle, stirring and dissolving, slowly dripping alkali liquor for reaction, dripping dilute acid until the pH value of the solution is 4-5 after the reaction is finished, and standing and separating to obtain regenerated hydroximic acid.
2. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: the volume ratio of the degraded waste compound extractant to the dilute acid in the step S1 is 1: 0.2-2, and the reaction time is 0.5-2 hours.
3. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: the diluted acid in the step S1 is one or a combination of 200-300 g/L sulfuric acid solution, 150-300 g/L hydrochloric acid solution and 50-150 g/L oxalic acid solution.
4. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: the alkaline solution in the step S3 is an alkaline solution prepared by sodium hydroxide and having a concentration of 50-300 g/L; the reaction time is 1-4 hours, and the standing time is 4-12 hours.
5. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: when the reflux reaction is performed in the step S4, the fatty acid: alcohol: acid catalyst ═ 1: 0.2-0.8: 0.2 to 0.4; the reflux reaction temperature is 80-84 ℃, and the reflux reaction time is 4-10 hours.
6. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: the alcohol in the step S4 is a C1-C3 low-carbon alcohol, preferably methanol; the acid catalyst is one of 98% concentrated sulfuric acid and 85% concentrated phosphoric acid, preferably 98% concentrated sulfuric acid.
7. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: the molar ratio of the fatty acid ester in the step S5 is as follows: hydroxylamine salts: base 1: (1.0-3): (1.5-3), preferably fatty acid ester: hydroxylamine salts: base 1: (1.0-2): (2-3).
8. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: in the step S5, the alkali solution is prepared from alkali and water, and the mass of the water is 0.8-2 times of that of the fatty acid ester.
9. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: the reaction process in the step S5 specifically comprises the steps of controlling the temperature of a reaction system to be lower than 30 ℃, slowly adding an alkali solution into a mixed system consisting of the fatty acid ester and the hydroxylamine salt aqueous solution in the step S4, reacting for 2-6 hours, raising the temperature to 40-65 ℃, and reacting for 2-6 hours.
10. The method for organic phase separation regeneration of a spent gallium and germanium extractant according to claim 1, wherein: the alkali in step S5 is one of sodium hydroxide or potassium hydroxide.
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