CN115386743B - Method for extracting tungsten from tungstate solution - Google Patents
Method for extracting tungsten from tungstate solution Download PDFInfo
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Abstract
The invention relates to tungsten metallurgy and tungsten chemical technology, in particular to a method for extracting tungsten from tungstate solution. The method for extracting tungsten from tungstate solution comprises the following steps: adjusting the pH value of the tungstate solution to be less than or equal to 2; extracting tungsten into the organic phase by using the organic phase extraction; washing with an acidic solution to remove impurities; then back-extracting with pure water to enable tungsten in the loaded organic phase to be selectively back-extracted into a water phase; tungsten is prepared from the meta-tungstic acid solution. The method can extract tungsten from tungstate solution without ammonia nitrogen, and simultaneously realize direct preparation of tungsten powder products.
Description
Technical Field
The invention relates to tungsten metallurgy and tungsten chemical technology, in particular to a method for extracting tungsten from tungstate solution.
Background
In the current tungsten metallurgy process, in order to prepare a tungsten product with the sodium impurity content reaching the standard, the conventional smelting method is to convert the sodium tungstate solution by ion exchange or solvent extraction to obtain an ammonium tungstate solution, and an ammonia nitrogen reagent is inevitably used, so that the discharge of ammonia nitrogen wastewater is unavoidable. In order to lead the ammonia nitrogen emission of the wastewater to reach the standard, the wastewater needs to be put into treatment, so that the tungsten smelting cost is increased. Therefore, the most reliable method for smelting tungsten is to avoid ammonia nitrogen. The current methods for extracting tungsten from tungstate solutions mainly comprise two types: (1) Extracting tungsten from a sodium tungstate solution by adopting a strong alkaline ion exchange resin or a quaternary ammonium salt extractant, and then desorbing or back-extracting by adopting ammonium salt to obtain an ammonium tungstate solution; (2) Extracting tungsten from the acidified sodium tungstate solution by adopting weak alkaline resin or tertiary amine or primary amine extractant, and then desorbing or back-extracting by adopting ammonia water to obtain ammonium tungstate solution. Both methods can effectively extract tungsten from tungstate solution, but the problem of ammonia nitrogen pollution is unavoidable. Moreover, these methods can only be used for preparing Ammonium Paratungstate (APT) which is a tungsten metallurgical product, and when tungsten oxide or tungsten powder is subsequently prepared from APT, a calcination process is also required. Because APT contains a certain amount of ammonium, waste gas containing ammonia nitrogen is inevitably generated during calcination, and the environment is polluted. Therefore, the industry needs to invest in the treatment of ammonia nitrogen pollution. In addition, APT is evaporated and crystallized from an ammonium tungstate solution, tungsten oxide is prepared through calcination, and then tungsten powder is obtained through reduction, so that the process is long, and the morphology and granularity control difficulty is high.
Therefore, no technology for extracting tungsten from tungstate solution effectively without ammonia nitrogen pollution exists in the tungsten-molybdenum smelting process at present.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems.
The invention provides a method for extracting tungsten from a tungstate solution, which can extract tungsten from the tungstate solution without ammonia nitrogen and simultaneously realize direct preparation of tungsten powder products.
A method of extracting tungsten from a tungstate solution, comprising:
s1: adjusting the pH value of the tungstate solution to be less than or equal to 2 to obtain a tungstate precursor solution;
s2: contacting the tungstate precursor solution with an organic phase to extract, so that tungsten in the tungstate precursor solution is extracted into the organic phase to obtain a loaded organic phase;
s3: washing the loaded organic phase with an acidic solution to remove impurities; then adding pure water to carry out back extraction on the loaded organic phase, so that tungsten in the loaded organic phase is selectively back extracted into a water phase to obtain a metatungstic acid solution;
s4: and preparing tungsten from the meta-tungstic acid solution.
According to an embodiment of the invention, step S1 adjusts the pH of the tungstate solution to a value of-1 to 2, specifically, for example, -1, -0.5, -0.2,0,0.2,0.5,1,2. It has been found that effective extraction of tungsten from the organic phase can be achieved by controlling the pH of the tungstate solution to 2 or less. The extraction under the condition can not only efficiently extract tungsten, but also effectively remove impurities in the solution.
According to the embodiment of the invention, the step S1 can be used for adjusting the pH value of the tungstate solution by using hydrochloric acid, sulfuric acid or nitric acid.
According to the embodiment of the invention, the tungstate solution comprises a sodium tungstate solution, a molybdenum-containing crude sodium tungstate solution, a potassium tungstate solution and the like.
According to the embodiment of the invention, the organic phase in the step S2 is formed by mixing an extracting agent and sulfonated kerosene.
According to the embodiment of the invention, the extractant is one or more selected from a neutral oxygen-containing extractant, a neutral phosphorus-containing extractant, an acidic phosphoric acid extractant and an oxime extractant.
According to the embodiment of the invention, the neutral oxygen-containing extractant is one or more selected from isooctyl alcohol, sec-octyl alcohol, isoamyl alcohol, ethyl acetate, MIBK, diethyl ether and the like.
According to the embodiment of the invention, the neutral phosphorus-containing extractant is selected from one or more of TBP, TOPO, TRPO and the like.
According to the embodiment of the invention, the acidic phosphoric acid extractant is one or more selected from P204, P507, CYANEX 272 and the like.
According to the embodiment of the invention, the oxime extractant is one or more selected from LIX63, HBL101 and the like.
According to an embodiment of the present invention, the content of the sulfonated kerosene in the organic phase is 10 to 95% (volume fraction), optionally 20 to 80% (volume fraction).
According to the embodiment of the invention, the extractant is a mixture of a neutral oxygen-containing extractant and a neutral phosphorus-containing extractant according to a volume ratio of 0-10:1.
According to the embodiment of the invention, the extractant is a mixture of a neutral oxygen-containing extractant and an acidic phosphoric acid extractant according to a volume ratio of 1:10-10:1.
According to the embodiment of the invention, the extractant is neutral phosphorus-containing extractant and acidic phosphoric acid extractant according to the volume ratio of 1:10-10: 1.
According to the embodiment of the invention, the extractant is a mixture of a neutral oxygen-containing extractant and an oxime extractant according to a volume ratio of 1:10-10:1.
According to the embodiment of the invention, the extractant is a mixture of a neutral phosphorus-containing extractant and an oxime extractant according to a volume ratio of 1:10-10:1.
According to an embodiment of the invention, the organic phase is mixed from 20 parts by volume of sec-octanol, 20 parts by volume of TBP and 60 parts by volume of sulfonated kerosene.
According to an embodiment of the invention, the organic phase is mixed from 60 parts by volume of TBP, 20 parts by volume of P204 and 20 parts by volume of sulfonated kerosene.
According to an embodiment of the invention, the organic phase is mixed from 30 parts by volume of isooctanol, 30 parts by volume of LIX63 and 40 parts by volume of sulfonated kerosene.
According to an embodiment of the invention, the organic phase is formed by mixing 80 parts by volume of TBP and 20 parts by volume of sulfonated kerosene.
The research shows that the extraction of tungsten in the solution and the subsequent removal of molybdenum can be efficiently completed by selecting the organic phase prepared from the extractant and the sulfonated kerosene.
According to an embodiment of the present invention, the volume ratio of the organic phase to the tungstate precursor solution in step S2 is (1:5) - (5:1), and is optionally (0.2-5): 1, or (1-2): 1.
According to an embodiment of the invention, the extraction temperature in step S2 is 20-60 ℃, optionally 20-50 ℃.
According to an embodiment of the invention, the extraction time in step S2 is 2-60 minutes, optionally 5-30 minutes.
According to an embodiment of the present invention, the acidic solution in step S3 is selected from one or more of hydrochloric acid (solution), sulfuric acid (solution), nitric acid (solution), and the like. Optionally, the concentration of the acidic solution is 0.2-2mol/L.
According to an embodiment of the present invention, the volume ratio of pure water to the loaded organic phase in step S3 is (3:1) - (1:1), (0.2-5): 1, alternatively (1-4): 1 or (2-3): 1.
According to an embodiment of the invention, the temperature of the stripping in step S3 is 20-60 ℃, optionally 20-50 ℃.
According to an embodiment of the invention, the time of the back extraction in step S3 is 2-60 minutes, optionally 5-30 minutes.
According to the embodiment of the invention, the method further comprises the step of repeating the step S2 to the step S3 so as to further reduce the impurity content of the metatungstic acid solution. Generally, the tungsten and impurity content after the complete crystallization of the metatungstic acid solution reaches the national standard GB/T3457-2013, and the metatungstic acid solution can be used for preparing tungsten.
According to the embodiment of the invention, the step S4 can be used for preparing tungsten from the metatungstic acid solution by any one of the following methods:
(1) Carrying out spray pyrolysis or spray drying on the metatungstic acid solution, and controlling the temperature to be 150-800 ℃ to directly obtain spherical tungsten oxide powder;
(2) Carrying out spray pyrolysis on the metatungstic acid solution, and directly obtaining spherical tungsten powder by using hydrogen as carrier gas and controlling the temperature to be 700-1400 ℃;
(3) Adding ammonia water into the metatungstic acid solution, controlling the molar ratio of the ammonia water to tungsten to be 1:2, and then drying to obtain ammonium metatungstate powder;
(4) Adding acid into the metatungstic acid solution, and controlling the reaction temperature to be 100-300 ℃ to convert the metatungstic acid into hydrated tungsten oxide;
(5) Adding hydrogen peroxide into the meta-tungstic acid solution to obtain a peroxytungstic acid solution, and then carrying out spray pyrolysis to obtain tungsten oxide, or carrying out hydrothermal decomposition to obtain hydrated tungsten oxide.
The term chinese-english contrast:
MIBK: methyl isobutyl ketone
TBP: tributyl phosphate
TOPO: trin-octyl phosphine oxide
TRPO: trialkyl phosphine oxides
P204: di (2-ethylhexyl) phosphate
P507: 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester
Cyanox 272: bis (2, 4-trimethylpentyl) phosphonic acid
LIX63:5, 8-diethyl-7-hydroxy-dodecane-6-oxime
HBL101:5, 8-diethyl-7-hydroxy-dodecane-6-one oxime.
N235: tri Xin Guiwan-base tertiary amine
The invention has at least one of the following beneficial effects:
1) Extracting and water back extracting from tungstate solution to obtain a metatungstic acid solution, and preparing the pure metatungstic acid solution for the first time.
2) Tungsten enrichment can be realized through water back extraction, ammonia nitrogen solution is not used for back extraction, and ammonia nitrogen wastewater discharge is completely eliminated.
3) Can directly realize the preparation of tungsten products from tungsten solution and realize the materialized metallurgy of tungsten.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
The present example provides a method of extracting tungsten from a tungstate solution:
the pH value of the crude potassium tungstate solution with the concentration of 150g/L is adjusted to 0.5 by using 1.5mol/L sulfuric acid solution to serve as a precursor solution; mixing 20 parts by volume of sec-octanol, 20 parts by volume of TBP and 60 parts by volume of sulfonated kerosene to prepare an organic phase; then mixing and extracting the organic phase and the precursor solution according to the volume ratio of 4:1 at the temperature of 30 ℃, and carrying out phase separation after extracting for 10 minutes to obtain a loaded organic phase and raffinate; the extraction rate of the detected tungsten is 98.5 percent (the raffinate adopts a cross-flow extraction mode to further extract the tungsten); the loaded organic phase is washed by adopting sulfuric acid solution with the concentration of 0.5mol/L, then pure water is used as a stripping agent for stripping according to the volume ratio of the loaded organic phase to the water phase of 2:1, the stripping temperature is controlled at 50 ℃, the stripping time is 30 minutes, the water phase is a metatungstic acid solution with the concentration of tungsten of 70.1g/L after detection, and the single-stage stripping rate is 95%. The solution of the meta-tungstic acid is added with 2mol/L sulfuric acid and then subjected to hydrothermal reaction at 200 ℃ to obtain hydrated tungsten oxide, and the conversion rate is 99.2%.
The reverse extraction operation mode of the loaded organic phase and the reverse extraction liquid can be adopted to further improve the reverse extraction rate of the tungsten in the loaded organic phase and the concentration of tungsten in the reverse extraction liquid.
Example 2
The present example provides a method of extracting tungsten from a tungstate solution:
the method comprises the steps of (1) adjusting the pH value of a molybdenum-containing crude sodium tungstate solution with tungsten trioxide concentration of 200g/L and Mo concentration of 10g/L to 0 by using a 2.0mol/L hydrochloric acid solution to serve as a precursor solution; mixing 60 parts by volume of TBP, 20 parts by volume of P204 and 20 parts by volume of sulfonated kerosene to prepare an organic phase; then mixing and extracting the organic phase and the precursor solution according to the volume ratio of the organic phase to the precursor solution of 2:1 at the temperature of 25 ℃, and carrying out phase separation after extracting for 20 minutes to obtain a loaded organic phase and raffinate; the extraction rate of tungsten is 94.5% and the extraction rate of molybdenum is 80% > (the raffinate adopts a countercurrent extraction mode to further extract tungsten and molybdenum); the loaded organic phase is washed by adopting a hydrochloric acid solution with the concentration of 0.5mol/L, then pure water is used as a stripping agent for stripping according to the volume ratio of the loaded organic phase to the water phase of 4:1, the stripping temperature is controlled at 40 ℃, the stripping time is 30 minutes, the water phase is a metatungstic acid solution with the concentration of tungsten of 264.6g/L after detection, and the single-stage stripping rate is 70%. The spherical tungsten oxide powder is prepared by directly carrying out spray pyrolysis on the metatungstic acid solution, and the conversion rate is 100%.
The reverse extraction operation mode of the reverse extraction is adopted for the loaded organic phase to further improve the reverse extraction rate of tungsten in the loaded organic phase. The molybdenum-loaded organic phase is subjected to back extraction by adopting 2mol/L ammonia water, the back extraction temperature of the back extraction organic phase is controlled to be 30 ℃ and the back extraction time is 30 minutes, and the detected water phase is an ammonium molybdate solution with the molybdenum concentration of 16g/L, and the single-stage back extraction rate is 100 percent. The strip liquor is further subjected to cross-flow strip for strip of another batch of molybdenum-loaded organic phase, so that the concentration of molybdenum in the strip liquor is increased.
Example 3
The present example provides a method of extracting tungsten from a tungstate solution:
the method comprises the steps of (1) adjusting the pH value of a molybdenum-containing crude sodium tungstate solution with the tungsten trioxide concentration of 50g/L and the Mo concentration of 0.5g/L to-1 by using a 2.0mol/L hydrochloric acid solution to obtain a precursor solution; then mixing 30 parts by volume of isooctanol, 30 parts by volume of LIX63 and 40 parts by volume of sulfonated kerosene to prepare an organic phase; then mixing and extracting the organic phase and the precursor solution according to the volume ratio of 1:1 at the temperature of 30 ℃, and carrying out phase separation after extracting for 20 minutes to obtain a loaded organic phase and raffinate; the extraction rate of tungsten is 97.8% and the extraction rate of molybdenum is 96% (the raffinate adopts a countercurrent extraction mode to further extract tungsten and molybdenum); the loaded organic phase is washed by adopting a nitric acid solution with the concentration of 0.5mol/L, then pure water is used as a stripping agent for stripping according to the volume ratio of the loaded organic phase to the water phase of 1:1, the stripping temperature is controlled at 50 ℃, the stripping time is 60 minutes, the water phase is detected to be a metatungstic acid solution with the concentration of tungsten of 45g/L, and the single-stage stripping rate is 92 percent. The metatungstic acid solution is added with hydrogen peroxide and then is thermally decomposed to prepare the tungstic acid, and the conversion rate is 99.8%.
The reverse extraction operation mode of the reverse extraction is adopted for the loaded organic phase to further improve the reverse extraction rate of tungsten in the loaded organic phase. The molybdenum-loaded organic phase is subjected to back extraction by adopting 3mol/L sodium hydroxide, the back extraction temperature of the back extraction organic phase is controlled to be 40 ℃ and the back extraction time is 20 minutes, and the detected water phase is sodium molybdate solution with the molybdenum concentration of 2.88g/L, and the single-stage back extraction rate is 100 percent. The sodium molybdate strip liquor is further subjected to cross-flow strip for strip of another batch of molybdenum-loaded organic phase, so that the concentration of molybdenum in the strip liquor is increased.
Example 4
The present example provides a method of extracting tungsten from a tungstate solution:
the pH value of the crude sodium tungstate solution with the concentration of 168g/L of tungsten trioxide is adjusted to be minus 0.2 by using 2.0mol/L of sulfuric acid solution, and the crude sodium tungstate solution is used as a precursor solution; then 80 parts by volume of TBP and 20 parts by volume of sulfonated kerosene are mixed to prepare an organic phase; then mixing and extracting the organic phase and the precursor solution according to the volume ratio of the organic phase to the precursor solution of 1:2 at the temperature of 30 ℃, and carrying out phase separation after extracting for 60 minutes to obtain a loaded organic phase and raffinate; the raffinate with the extraction rate of 56% of tungsten is detected to further extract tungsten in a cross-flow extraction mode; washing the loaded organic phase by adopting a sulfuric acid solution with the concentration of 1mol/L, then carrying out back extraction by using pure water as a back extraction agent according to the volume ratio of the loaded organic phase to the water phase of 1:2, controlling the back extraction temperature at 40 ℃, controlling the back extraction time at 30 minutes, and detecting that the water phase is a metatungstic acid solution with the concentration of 154.8g/L, wherein the single-stage back extraction rate is 96%. Adding ammonia water into the metatungstic acid solution, and spray drying to obtain ammonium metatungstate powder with a conversion rate of 99.7%.
The reverse extraction operation mode of the reverse extraction is adopted for the loaded organic phase to further improve the reverse extraction rate of tungsten in the loaded organic phase.
Comparative example 1
The only difference from example 1 is that: the pH value of the crude potassium tungstate solution with the concentration of 150g/L is adjusted to 4 by using 1.5mol/L sulfuric acid solution to be used as a precursor solution; after extraction with the organic phase, the extraction yield of tungsten was 0.2% and tungsten was not substantially extracted.
Comparative example 2
The only difference from example 1 is that: the loaded organic phase is washed by adopting sulfuric acid solution with the concentration of 0.5mol/L, then ammonia water is used as a stripping agent for stripping according to the ratio of the organic phase to the water of 2:1, the stripping temperature is controlled at 50 ℃, the stripping time is 30 minutes, the detected water phase is ammonium tungstate solution with the concentration of 73.9g/L, and the single-stage stripping rate is 100 percent. A solution of metatungstic acid could not be obtained.
Comparative example 3
The only difference from example 1 is that: the solution of the meta-tungstic acid is added with 1mol/L sulfuric acid and then subjected to hydrothermal reaction at 800 ℃ to obtain hydrated tungsten oxide, and the conversion rate is 56.2%.
Comparative example 4
The only difference from example 1 is that: the organic phase was replaced with 30 parts by volume of N235 (tri Xin Guiwan-base tertiary amine) and 70 parts by volume of sulfonated kerosene, the extraction rate of tungsten was 98%, and when the stripping was performed with water, the stripping rate of tungsten was 0.1%, which was hardly stripped.
The above results indicate that the tungstate solution must be pH controlled to 2 or less, otherwise tungsten cannot be extracted efficiently by the organic phase. In the back extraction process, ammonia water or sodium hydroxide solution is adopted to effectively carry out back extraction on tungsten loaded on an organic phase, but a metatungstic acid solution cannot be obtained. The metatungstic acid solution obtained by the method only contains tungsten, oxygen and hydrogen elements, and is very suitable for preparing tungsten powder products in a follow-up cleaning way.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (12)
1. A method of extracting tungsten from a tungstate solution, comprising:
s1: adjusting the pH value of the tungstate solution to be less than or equal to 2 to obtain a tungstate precursor solution;
s2: contacting the tungstate precursor solution with an organic phase to extract, so that tungsten in the tungstate precursor solution is extracted into the organic phase to obtain a loaded organic phase; the organic phase is formed by mixing an extractant and sulfonated kerosene; the extractant is one or more selected from neutral oxygen-containing extractant, neutral phosphorus-containing extractant, acidic phosphoric acid extractant and oxime extractant;
s3: washing the loaded organic phase with an acidic solution to remove impurities; then adding pure water to carry out back extraction on the loaded organic phase, so that tungsten in the loaded organic phase is selectively back extracted into a water phase to obtain a metatungstic acid solution;
s4: preparing tungsten from the metatungstic acid solution by any one of the following methods;
(1) Carrying out spray pyrolysis or spray drying on the metatungstic acid solution, and controlling the temperature to be 150-800 ℃ to directly obtain spherical tungsten oxide powder; or alternatively, the first and second heat exchangers may be,
(2) Carrying out spray pyrolysis on the metatungstic acid solution, and directly obtaining spherical tungsten powder by using hydrogen as carrier gas and controlling the temperature to be 700-1400 ℃; or alternatively, the first and second heat exchangers may be,
(3) Adding ammonia water into the metatungstic acid solution, controlling the molar ratio of the ammonia water to tungsten to be 1:2, and then drying to obtain ammonium metatungstate powder; or alternatively, the first and second heat exchangers may be,
(4) Adding acid into the metatungstic acid solution, and controlling the reaction temperature to be 100-300 ℃ to convert the metatungstic acid into hydrated tungsten oxide; or alternatively, the first and second heat exchangers may be,
(5) Adding hydrogen peroxide into the meta-tungstic acid solution to obtain a peroxytungstic acid solution, and then carrying out spray pyrolysis to obtain tungsten oxide, or carrying out hydrothermal decomposition to obtain hydrated tungsten oxide.
2. The method of extracting tungsten from a tungstate solution as claimed in claim 1, wherein the step S1 adjusts a pH value of the tungstate solution to-1 to 2.
3. The method of extracting tungsten from a tungstate solution as claimed in claim 1, wherein the step S1 adjusts pH of the tungstate solution to-1, -0.5, -0.2,0,0.2,0.5,1 or 2.
4. The method for extracting tungsten from tungstate solution according to claim 1, wherein the neutral oxygen-containing extractant is one or more selected from isooctanol, sec-octanol, isoamyl alcohol, ethyl acetate, MIBK, diethyl ether; and/or the number of the groups of groups,
the neutral phosphorus-containing extractant is one or more selected from TBP, TOPO, TRPO; and/or the number of the groups of groups,
the acidic phosphoric acid extractant is one or more selected from P204, P507 and CYANEX 272; and/or the number of the groups of groups,
the oxime extractant is one or more selected from LIX63 and HBL 101.
5. The method of extracting tungsten from a tungstate solution as claimed in claim 1 or 4, wherein a volume fraction of the sulfonated kerosene in the organic phase is 10 to 95%.
6. The method of extracting tungsten from a tungstate solution as claimed in claim 5, wherein the volume fraction of the sulfonated kerosene in the organic phase is 20-80%.
7. The method of extracting tungsten from a tungstate solution as claimed in claim 1, wherein the extractant is selected from any one of the following:
the extractant is a mixture of a neutral oxygen-containing extractant and a neutral phosphorus-containing extractant according to the volume ratio of 0-10:1; or alternatively, the first and second heat exchangers may be,
the extractant is a mixture of a neutral oxygen-containing extractant and an acidic phosphoric acid extractant according to the volume ratio of 1:10-10:1; or alternatively, the first and second heat exchangers may be,
the extractant is neutral phosphorus extractant and acidic phosphoric acid extractant according to the volume ratio of 1:10-10:1, a mixture of two or more of the above-mentioned materials; or alternatively, the first and second heat exchangers may be,
the extractant is a mixture of a neutral oxygen-containing extractant and an oxime extractant according to the volume ratio of 1:10-10:1; or alternatively, the first and second heat exchangers may be,
the extractant is prepared by mixing a neutral phosphorus-containing extractant and an oxime extractant according to a volume ratio of 1:10-10:1.
8. The method of extracting tungsten from a tungstate solution according to claim 1 or 2, wherein the organic phase of step S2 is selected from any one of the following:
the organic phase is formed by mixing 20 parts by volume of sec-octanol, 20 parts by volume of TBP and 60 parts by volume of sulfonated kerosene; or alternatively, the first and second heat exchangers may be,
the organic phase is formed by mixing 60 parts by volume of TBP, 20 parts by volume of P204 and 20 parts by volume of sulfonated kerosene; or alternatively, the first and second heat exchangers may be,
the organic phase is formed by mixing 30 parts by volume of isooctanol, 30 parts by volume of LIX63 and 40 parts by volume of sulfonated kerosene; or alternatively, the first and second heat exchangers may be,
the organic phase is formed by mixing 80 parts by volume of TBP and 20 parts by volume of sulfonated kerosene.
9. The method of extracting tungsten from a tungstate solution as claimed in claim 1,
the volume ratio of the organic phase to the tungstate precursor solution in the step S2 is (0.2-5) 1; and/or the number of the groups of groups,
the extraction temperature in the step S2 is 20-60 ℃; and/or the number of the groups of groups,
the extraction time in the step S2 is 2-60 minutes; and/or the number of the groups of groups,
the acidic solution in the step S3 is one or more selected from hydrochloric acid solution, sulfuric acid solution and nitric acid solution; and/or the number of the groups of groups,
the volume ratio of the pure water to the loaded organic phase in the step S3 is (0.2-5): 1; and/or the number of the groups of groups,
the temperature of the back extraction in the step S3 is 20-60 ℃; and/or the number of the groups of groups,
the back extraction time in the step S3 is 2-60 minutes.
10. The method of extracting tungsten from a tungstate solution as claimed in claim 9,
the volume ratio of the organic phase to the tungstate precursor solution in the step S2 is (1-2) 1; and/or the number of the groups of groups,
the extraction temperature in the step S2 is 20-50 ℃; and/or the number of the groups of groups,
the extraction time in the step S2 is 5-30 minutes; and/or the number of the groups of groups,
the concentration of the acid solution in the step S3 is 0.2-2mol/L; and/or the number of the groups of groups,
the volume ratio of the pure water to the loaded organic phase in the step S3 is (1-4): 1; and/or the number of the groups of groups,
the temperature of the back extraction in the step S3 is 20-50 ℃; and/or the number of the groups of groups,
the back extraction time in the step S3 is 5-30 minutes.
11. The method of extracting tungsten from a tungstate solution as claimed in claim 9, wherein a volume ratio of the pure water to the loaded organic phase in the step S3 is (2-3): 1.
12. The method of extracting tungsten from a tungstate solution as claimed in any one of claims 1 to 4, further comprising repeating steps S2 to S3 to further reduce an impurity content of the metatungstic acid solution.
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