CN112226634A - Method for extracting and separating tungsten and molybdenum in aqueous solution by using aqueous two-phase system - Google Patents
Method for extracting and separating tungsten and molybdenum in aqueous solution by using aqueous two-phase system Download PDFInfo
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Abstract
The invention provides a method for extracting and separating tungsten and molybdenum in an aqueous solution by using a two-aqueous-phase system, belonging to the technical field of metallurgy. Firstly, mixing aqueous solution containing paratungstic acid B and molybdate with nitrogen-containing nonionic surfactant and sodium sulfate to obtain mixed solution; and then adjusting the mixed solution into a weakly acidic mixed solution, extracting at the temperature of 60-80 ℃, collecting a surfactant phase, namely a tungsten-rich phase, and collecting a water phase, namely a molybdenum-rich phase. The method provided by the invention has higher extraction efficiency, the single-stage extraction rate of tungsten can reach more than 97 percent, the lowest extraction rate is 84.47 percent, the single-stage extraction rate of molybdenum is below 38.36 percent, and the highest separation factor of tungsten and molybdenum can reach 77.34.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for extracting and separating tungsten and molybdenum in an aqueous solution by using a two-aqueous-phase system.
Background
Tungsten and molybdenum play an extremely important role in many technical fields. Tungsten is the highest melting metal, widely used for drawing the filament of a bulb, and has the reputation of "photophobia"; meanwhile, the tungsten ore is also an important strategic metal in the world, and the tungsten ore is called as 'heavy stone' in ancient times; about 50% of tungsten ores mined in the world are used for smelting high-quality steel, about 35% are used for producing hard steel, about 10% are used for manufacturing tungsten wires, and about 5% are used for other purposes. Molybdenum is often used as an additive for producing various alloy steels in the metallurgical industry, or forms high-grade alloys with tungsten, nickel, cobalt, zirconium, titanium, vanadium, rhenium and the like so as to improve the high-temperature strength, the wear resistance and the corrosion resistance of the alloys; in molybdenum chemical products, molybdenum-containing pigments have many excellent properties, for example, molybdenum yellow has the advantages of bright color and good photo-thermal stability, and is widely applied to coatings such as common paints, high-grade paints, building coatings and the like.
In recent years, with the rapid increase of demand for tungsten and molybdenum metals, people pay more attention to recycling the metals from secondary resources. For example, it is recovered and purified from a spent catalyst in petroleum refining. However, tungsten and molybdenum belong to the same subgroup and are affected by "lanthanide contraction", and the atomic radii, atomic structures, and chemical properties of both are very similar, so that separation of molybdenum from impurities in tungsten-containing solutions is most difficult. The existing methods for extracting and separating tungsten and molybdenum comprise a precipitation method, an ion exchange method and a solvent extraction method, wherein the solvent extraction method can effectively separate tungsten and molybdenum, has low cost and mature industrial application, but the method usually uses a large amount of organic solvents in the operation process and does not conform to the current green chemical concept. The prior art CN108588415A proposes a method for extracting and separating tungsten in an aqueous solution by using a two-aqueous-phase system, which avoids the use of an organic solvent, but cannot effectively separate tungsten and molybdenum when the method is used for the aqueous solution containing tungsten and molybdenum.
Disclosure of Invention
The invention aims to provide a method for extracting and separating tungsten and molybdenum in an aqueous solution by using a two-aqueous-phase system, which can effectively separate tungsten and molybdenum in the aqueous solution containing sec-tungstic acid B and molybdate, does not need to use an organic solvent, and is a green and environment-friendly process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for extracting and separating tungsten and molybdenum in an aqueous solution by using a two-aqueous-phase system, which comprises the following steps:
mixing an aqueous solution containing sec-tungstic acid B and molybdate with a nitrogen-containing nonionic surfactant and sodium sulfate to obtain a mixed solution;
adjusting the mixed solution to be weakly acidic, extracting at the temperature of 60-80 ℃, collecting an organic phase, namely a tungsten-rich phase, and collecting a water phase, namely a molybdenum-rich phase; the pH value of the weakly acidic mixed solution is 6.2-7.0.
Preferably, the nitrogen-containing nonionic surfactant is at least one of octadecylamine polyoxyethylene (5) ether, octadecylamine polyoxyethylene (10) ether, octadecylamine polyoxyethylene (15) ether, octadecylamine polyoxyethylene (30) ether, dodecylamine polyoxyethylene (5) ether, dodecylamine polyoxyethylene (10) ether and dodecylamine polyoxyethylene (15) ether.
Preferably, the content of the nitrogen-containing nonionic surfactant in the mixed solution is 10-30 wt%, and the content of the sodium sulfate is 10-20 wt%.
Preferably, the content of the nitrogen-containing nonionic surfactant in the mixed solution is 10-20 wt%.
Preferably, the pH value of the weakly acidic mixed solution is 6.6-7.0.
Preferably, the extraction comprises stirring mixing and standing phase separation which are carried out in sequence.
Preferably, the stirring and mixing time is 30-60 min.
Preferably, the standing phase separation time is 30-120 min.
Preferably, the standing phase separation time is 60-120 min.
Preferably, the content of tungsten element in the mixed solution is 0.1-3.0 wt%, and the content of molybdenum element is 0.1-2.0 wt%.
The invention provides a method for extracting and separating tungsten and molybdenum from an aqueous solution by using an aqueous two-phase system, which is characterized in that a nitrogen-containing nonionic surfactant and sodium sulfate are added into the aqueous solution, the mixed solution is adjusted to be weakly acidic, tungsten elements exist in the form of paratungstic acid B anions, molybdenum exists in the form of single molybdate ions, the hydrophobicity of the paratungstic acid B anions is far higher than that of the single molybdate ions, under the condition of 60-80 ℃, the nitrogen-containing nonionic surfactant forms a micellar phase due to the existence of the sodium sulfate and forms an aqueous two-phase system with a water phase, the paratungstic acid B anions can enter the relatively hydrophobic surfactant micellar phase (namely, the nitrogen-containing nonionic surfactant micelles), and the single molybdate ions are remained in the water phase. The experimental result shows that the method provided by the invention has higher extraction efficiency, the single-stage extraction rate of tungsten is above 84.47%, the single-stage extraction rate of molybdenum is below 38.36%, and the separation factors of tungsten and molybdenum are above 60.22 and can reach 77.34 to the maximum extent.
Detailed Description
The invention provides a method for extracting and separating tungsten and molybdenum in an aqueous solution by using a two-aqueous-phase system, which comprises the following steps:
mixing an aqueous solution containing sec-tungstic acid B and molybdate with a nitrogen-containing nonionic surfactant and sodium sulfate to obtain a mixed solution;
and adjusting the mixed solution into a weakly acidic mixed solution, then extracting at the temperature of 60-80 ℃, collecting a surfactant phase, namely a tungsten-rich phase, and collecting a water phase, namely a molybdenum-rich phase.
The invention mixes the water solution containing the paratungstic acid B and the molybdate with the nitrogen-containing nonionic surfactant and the sodium sulfate to obtain the mixed solution.
The source of the aqueous solution containing the paratungstic acid B and the molybdate is not particularly limited, and the aqueous solution containing the paratungstic acid B and the molybdate can be produced in any treatment process, for example, in the purification process of sodium tungstate crystal containing the molybdate, the sodium tungstate crystal is dissolved in water, then is acidified to obtain the paratungstic acid A, and then is catalyzed to produce the aqueous solution containing the paratungstic acid B and the molybdate. In the embodiment of the invention, the aqueous solution containing the paratungstic acid B and the molybdate is preferably a mixed solution of the aqueous solution of the paratungstic acid B and the molybdate; the molybdate is preferably sodium molybdate; the concentrations of the aqueous solution of paratungstic acid B and the aqueous solution of molybdate are not particularly limited in the present invention. In the embodiment of the invention, the concentrations of the paratungstic acid B and the molybdate are calculated according to the contents of tungsten and molybdenum, specifically, the content of tungsten in the mixed solution is preferably 0.1-3.0 wt%, and the content of molybdenum is preferably 0.1-2.0 wt%.
In the present invention, the nitrogen-containing nonionic surfactant is preferably at least one of octadecylamine polyoxyethylene (5) ether (AC1805), octadecylamine polyoxyethylene (10) ether (AC1810), octadecylamine polyoxyethylene (15) ether (AC1815), octadecylamine polyoxyethylene (30) ether (AC1830), dodecylamine polyoxyethylene (5) ether (AC1205), dodecylamine polyoxyethylene (10) ether (AC1210), and dodecylamine polyoxyethylene (15) ether (AC 1215); more preferably octadecylamine polyoxyethylene (5) ether (AC1805), octadecylamine polyoxyethylene (10) ether (AC1810), octadecylamine polyoxyethylene (15) ether (AC1815), octadecylamine polyoxyethylene (30) ether (AC1830), dodecylamine polyoxyethylene (5) ether (AC1205), dodecylamine polyoxyethylene (10) ether (AC1210) or dodecylamine polyoxyethylene (15) ether (AC 1215). In the invention, the nitrogen-containing nonionic surfactant has certain hydrophobicity, and can form a surfactant micelle phase at 60-80 ℃ in the presence of sodium sulfate, and the surfactant micelle phase is separated from a water phase, so that secondary tungstic acid B anions can be extracted from the water phase.
In the invention, the content of the nitrogen-containing nonionic surfactant in the mixed solution is preferably 10-30 wt%, and more preferably 10-20 wt%.
In the present invention, the content of sodium sulfate in the mixed solution is preferably 10 wt%. The adding mode of the sodium sulfate is not particularly limited, the sodium sulfate can be added in the form of a sodium sulfate solid or in the form of a sodium sulfate aqueous solution, and the concentration of the sodium sulfate in the mixed solution can be in the range; in the present examples, the sodium sulfate is preferably added in the form of an aqueous solution of sodium sulfate. In the present invention, the hydration of the sodium sulfate promotes phase separation and lowers the phase separation temperature.
In the present invention, when the content of each substance in the mixed solution obtained by mixing the aqueous solution containing the sec-tungstic acid B and the molybdate with the nitrogen-containing nonionic surfactant and sodium sulfate is higher than the above-mentioned preferable range, it is preferable to add water and adjust the concentration of the mixed solution obtained to be within the preferable range; the water is preferably deionized water.
After the mixed solution is obtained, the mixed solution is adjusted to be weakly acidic, then extraction is carried out at the temperature of 60-80 ℃, a surfactant phase is collected, namely a tungsten-rich phase, and a water phase is collected, namely a molybdenum-rich phase.
In the present invention, the pH of the weakly acidic mixed solution is preferably 6.2 to 7.0, and more preferably 6.6. In the invention, the weakly acidic condition can ensure that tungsten exists in the form of paratungstic acid B anions and molybdenum exists in the form of single molybdate radical ions, so as to be beneficial to subsequent extraction and phase separation. The type of the pH adjuster used for the adjustment is not particularly limited in the present invention, and may be within the above range, and in the embodiment of the present invention, the pH adjuster is preferably an acid solution, more preferably sulfuric acid, nitric acid, or hydrochloric acid, and still more preferably sulfuric acid; the concentration of the sulfuric acid is preferably 6 mol/L.
In the invention, the extraction preferably comprises stirring, mixing and standing for phase separation, wherein the stirring and mixing time is preferably 30-600 min; the stirring speed is not specially limited, and the stirring uniformity can be ensured; the time for standing and phase separation is preferably 30-120 min, and more preferably 60-120 min.
The tungsten-rich phase can be further processed by those skilled in the art to obtain pure tungsten products, such as by stripping tungsten or molybdenum from the tungsten-rich phase with aqueous ammonium sulfate or ammonium carbonate (see "partition properties of vanadium-molybdenum-tungsten in nonionic surfactant bi-aqueous system", doctor's paper, zhangyongqiang; "research on TX-100 bi-aqueous system and its extraction w (vi)", master's paper, ludrang strength).
The following examples are provided to illustrate the method for extracting and separating tungsten and molybdenum from an aqueous solution containing paratungstic acid B and molybdate, but should not be construed as limiting the scope of the present invention.
Example 1
Mixing AC1805, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1805 is 20 wt%, the content of tungsten element is 0.1 wt%, the content of molybdenum element is 0.1 wt%, and the content of sodium sulfate is 10 wt%;
regulating the mixed solution to a mixed solution with the pH value of 6.6 by using sulfuric acid with the concentration of 6mol/L, heating to 80 ℃, stirring for 30min for extraction, standing for 30min at 80 ℃ for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the aqueous phase were measured by an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (i.e., the mass percentage of tungsten or molybdenum extracted to the upper phase to tungsten or molybdenum in the mixed solution) were calculated, with the result that the extraction rate of tungsten was 87.03%, the extraction rate of molybdenum was 10.03%, and the separation factor of tungsten and molybdenum was calculated to be 60.22.
Example 2
Mixing AC1810, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1810 is 20 wt%, the content of tungsten element is 0.1 wt%, the content of molybdenum element is 1.0 wt%, and the content of sodium sulfate is 20 wt%;
regulating the mixed solution to a mixed solution with the pH value of 6.2 by using sulfuric acid with the concentration of 6mol/L, heating to 80 ℃, stirring for 60min for extraction, standing at 80 ℃ for 120min for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the lower phase are tested by adopting an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (namely the tungsten or molybdenum extracted to the upper phase accounts for the mass percent of the tungsten or molybdenum in the mixed solution) are calculated, so that the extraction rate of tungsten is 90.78%, the extraction rate of molybdenum is 16.19%, and the tungsten-molybdenum separation factor is calculated to be 71.26.
Example 3
Mixing AC1815, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1815 is 20 wt%, the content of tungsten element is 0.1 wt%, the content of molybdenum element is 2.0 wt%, and the content of sodium sulfate is 15 wt%;
regulating the mixed solution to be mixed solution with the pH value of 7.0 by using sulfuric acid with the concentration of 6mol/L, then heating to 80 ℃, stirring for 30min for extraction, standing for 60min at 80 ℃ for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the aqueous phase were measured by an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (i.e., the mass percentage of tungsten or molybdenum extracted into the upper phase to the tungsten or molybdenum in the mixed solution) were calculated, with the result that the extraction rate of tungsten was 91.27%, the extraction rate of molybdenum was 15.97%, and the tungsten-molybdenum separation factor was calculated to be 77.34.
Example 4
Mixing AC1830, aqueous solution of paratungstic acid B, aqueous solution of sodium molybdate, aqueous solution of sodium sulfate and deionized water to obtain mixed solution; wherein, the content of AC1830 is 20 wt%, the content of tungsten element is 3.0 wt%, the content of molybdenum element is 0.1 wt%, the content of sodium sulfate is 10 wt%;
regulating the mixed solution to be mixed solution with the pH value of 7.0 by using sulfuric acid with the concentration of 6mol/L, then heating to 80 ℃, stirring for 30min for extraction, standing for 30min at 80 ℃ for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the water phase are tested by adopting an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (namely, the tungsten or molybdenum extracted to the upper phase accounts for the mass percent of the tungsten or molybdenum in the mixed solution) are calculated, so that the extraction rate of tungsten is 84.47%, the extraction rate of molybdenum is 7.10%, and the tungsten-molybdenum separation factor is calculated to be 71.19.
Example 5
Mixing AC1205, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1205 is 20 wt%, the content of tungsten element is 3.0 wt%, the content of molybdenum element is 1.0 wt%, and the content of sodium sulfate is 15 wt%;
regulating the mixed solution to a mixed solution with the pH value of 6.6 by using sulfuric acid with the concentration of 6mol/L, heating to 60 ℃, stirring for 30min for extraction, standing at 60 ℃ for 120min for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the aqueous phase were tested by an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (i.e., the mass percentage of tungsten or molybdenum extracted to the upper phase to tungsten or molybdenum in the mixed solution) were calculated, with the result that the extraction rate of tungsten was 96.60%, the extraction rate of molybdenum was 31.39%, and the tungsten-molybdenum separation factor was calculated to be 72.14.
Example 6
Mixing AC1210, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1210 is 20 wt%, the content of tungsten element is 3.0 wt%, the content of molybdenum element is 2.0 wt%, and the content of sodium sulfate is 20 wt%;
regulating the mixed solution to a mixed solution with the pH value of 6.6 by using sulfuric acid with the concentration of 6mol/L, heating to 70 ℃, stirring for 30min for extraction, standing at 70 ℃ for 60min for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the aqueous phase were tested by an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (i.e., the mass percentage of tungsten or molybdenum extracted to the upper phase to tungsten or molybdenum in the mixed solution) were calculated, with the result that the extraction rate of tungsten was 97.59%, the extraction rate of molybdenum was 38.36%, and the tungsten-molybdenum separation factor was calculated to be 73.20.
Example 7
Mixing AC1215, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1215 is 20 wt%, the content of tungsten element is 2.0 wt%, the content of molybdenum element is 0.5 wt%, and the content of sodium sulfate is 10 wt%;
regulating the mixed solution to a mixed solution with the pH value of 6.6 by using sulfuric acid with the concentration of 6mol/L, heating to 80 ℃, stirring for 30min for extraction, standing at 80 ℃ for 120min for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the water phase are tested by adopting an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (namely, the tungsten or molybdenum extracted to the upper phase accounts for the mass percent of the tungsten or molybdenum in the mixed solution) are calculated, so that the extraction rate of tungsten is 93.53%, the extraction rate of molybdenum is 20.55%, and the tungsten-molybdenum separation factor is calculated to be 71.85.
Example 8
Mixing AC1815, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1815 is 10 wt%, the content of tungsten element is 2.0 wt%, the content of molybdenum element is 0.5 wt%, and the content of sodium sulfate is 15 wt%;
regulating the mixed solution to a mixed solution with the pH value of 6.6 by using sulfuric acid with the concentration of 6mol/L, heating to 80 ℃, stirring for 30min for extraction, standing for 30min at 80 ℃ for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the aqueous phase were measured by an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (i.e., the mass percentage of tungsten or molybdenum extracted to the upper phase to tungsten or molybdenum in the mixed solution) were calculated, with the result that the extraction rate of tungsten was 91.69%, the extraction rate of molybdenum was 17.95%, and the tungsten-molybdenum separation factor was calculated to be 67.73.
Example 9
Mixing AC1815, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1815 is 30 wt%, the content of tungsten element is 2.0 wt%, the content of molybdenum element is 0.5 wt%, and the content of sodium sulfate is 20 wt%;
regulating the mixed solution to a mixed solution with the pH value of 6.6 by using sulfuric acid with the concentration of 6mol/L, heating to 80 ℃, stirring for 30min for extraction, standing at 80 ℃ for 120min for phase separation, taking an upper phase (namely a surfactant phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the water phase are tested by adopting an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (namely, the tungsten or molybdenum extracted to the upper phase accounts for the mass percent of the tungsten or molybdenum in the mixed solution) are calculated, so that the extraction rate of tungsten is 93.47%, the extraction rate of molybdenum is 20.88%, and the tungsten-molybdenum separation factor is calculated to be 69.35.
Comparative example 1
Mixing polyethylene glycol (PEG2000), aqueous solution of paratungstic acid B, aqueous solution of sodium molybdate, aqueous solution of sodium sulfate and deionized water to obtain mixed solution; wherein the content of PEG2000 is 20 wt%, the content of tungsten element is 2.0 wt%, the content of molybdenum element is 0.5 wt%, and the content of sodium sulfate is 10 wt%;
regulating the mixed solution to a mixed solution with the pH value of 3.0 by using sulfuric acid with the concentration of 6mol/L, then heating to 40 ℃, stirring for 30min for extraction, and standing for 60min at 40 ℃ for phase separation.
The contents of tungsten and molybdenum in the aqueous phase are tested by adopting an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (namely the mass percentage of the tungsten or molybdenum in the extracted aqueous phase to the tungsten or molybdenum in the mixed solution) are calculated, so that the extraction rate of tungsten is 98.65%, the extraction rate of molybdenum is 97.48%, and the tungsten-molybdenum separation factor is calculated to be 1.36.
Comparative example 2
Mixing polyoxyethylene polyoxypropylene polyoxyethylene block copolymer (L35), aqueous solution of paratungstic acid B, aqueous solution of sodium molybdate, aqueous solution of sodium sulfate and deionized water to obtain mixed solution; wherein the content of L35 is 20 wt%, the content of tungsten element is 2.0 wt%, the content of molybdenum element is 0.5 wt%, and the content of sodium sulfate is 10 wt%;
regulating the mixed solution to a mixed solution with the pH value of 3.0 by using sulfuric acid with the concentration of 6mol/L, then heating to 40 ℃, stirring for 30min for extraction, and standing for 60min at 40 ℃ for phase separation.
The contents of tungsten and molybdenum in the lower phase are tested by adopting an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (namely the mass percentage of tungsten or molybdenum in the extracted water phase to the tungsten or molybdenum in the mixed solution) are calculated, so that the extraction rate of tungsten is 98.33%, the extraction rate of molybdenum is 97.17%, and the tungsten-molybdenum separation factor is calculated to be 1.66.
Comparative example 3
Mixing AC1815, a paratungstic acid B aqueous solution, a sodium molybdate aqueous solution, a sodium sulfate aqueous solution and deionized water to obtain a mixed solution; wherein, the content of AC1815 is 20 wt%, the content of tungsten element is 2.0 wt%, the content of molybdenum element is 0.5 wt%, and the content of sodium sulfate is 10 wt%;
regulating the mixed solution to a mixed solution with the pH value of 5.0 by using sulfuric acid with the concentration of 6mol/L, then heating to 80 ℃, stirring for 30min for extraction, standing at 80 ℃ for 120min for phase separation, taking an upper phase (namely an organic phase) as a tungsten-rich phase, and taking a lower phase (namely a water phase) as a molybdenum-rich phase.
The contents of tungsten and molybdenum in the water phase are tested by adopting an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (namely, the tungsten or molybdenum extracted to the upper phase accounts for the mass percent of the tungsten or molybdenum in the mixed solution) are calculated, so that the extraction rate of tungsten is 99.91 percent, the extraction rate of molybdenum is 99.07 percent, and the tungsten-molybdenum separation factor is calculated to be 1.09.
Comparative example 4
Mixing polyethylene glycol octyl phenyl ether (Triton X-100), aqueous solution of paratungstic acid B, aqueous solution of sodium molybdate, aqueous solution of sodium sulfate and deionized water to obtain mixed solution; wherein the content of Triton X-100 is 20 wt%, the content of tungsten element is 2.0 wt%, the content of molybdenum element is 0.5 wt%, and the content of sodium sulfate is 10 wt%;
adjusting the mixed solution to a mixed solution with the pH value of 6.6 by using sulfuric acid with the concentration of 6mol/L, then heating to 40 ℃, stirring for 30min for extraction, and standing for 60min at 40 ℃ for phase separation.
The contents of tungsten and molybdenum in the lower phase are tested by adopting an inductively coupled plasma mass spectrometer, and then the extraction rates of tungsten and molybdenum (namely the mass percentage of tungsten or molybdenum in the extracted water phase to the tungsten or molybdenum in the mixed solution) are calculated, so that the extraction rate of tungsten is 98.64 percent, the extraction rate of molybdenum is 97.73 percent, and the tungsten-molybdenum separation factor is calculated to be 0.96.
According to the embodiment and the comparative example, the method controls the type, the extraction temperature and the pH value of the nonionic surfactant, utilizes the fact that the nitrogenous nonionic surfactant has certain hydrophobicity, can form a surfactant micelle phase at 60-80 ℃ in the presence of sodium sulfate, and can extract the secondary tungstic acid B anions from the water phase by separating the surfactant micelle phase from the water phase, so that the tungsten and the molybdenum can be efficiently separated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for extracting and separating tungsten and molybdenum in an aqueous solution by using a two-aqueous-phase system is characterized by comprising the following steps:
mixing an aqueous solution containing sec-tungstic acid B and molybdate with a nitrogen-containing nonionic surfactant and sodium sulfate to obtain a mixed solution;
adjusting the mixed solution to be weakly acidic, extracting at the temperature of 60-80 ℃, collecting an organic phase, namely a tungsten-rich phase, and collecting a water phase, namely a molybdenum-rich phase; the pH value of the weakly acidic mixed solution is 6.2-7.0.
2. The method of claim 1, wherein the nitrogen-containing nonionic surfactant is at least one of an octadecyl amine polyoxyethylene (5) ether, an octadecyl amine polyoxyethylene (10) ether, an octadecyl amine polyoxyethylene (15) ether, an octadecyl amine polyoxyethylene (30) ether, a dodecyl amine polyoxyethylene (5) ether, a dodecyl amine polyoxyethylene (10) ether, and a dodecyl amine polyoxyethylene (15) ether.
3. The method according to claim 1 or 2, wherein the mixed solution contains 10 to 30 wt% of the nitrogen-containing nonionic surfactant and 10 to 20 wt% of sodium sulfate.
4. The method according to claim 1, wherein the content of the nitrogen-containing nonionic surfactant in the mixed solution is 10 to 20 wt%.
5. The method as claimed in claim 1, wherein the pH of the weakly acidic mixed solution is 6.6 to 7.0.
6. The method of claim 1, wherein the extraction comprises sequential stirred mixing and standing phase separation.
7. The method according to claim 6, wherein the stirring and mixing time is 30-60 min.
8. The method according to claim 6, wherein the standing phase separation time is 30-120 min.
9. The method according to claim 8, wherein the standing phase separation time is 60-120 min.
10. The method according to claim 1, wherein the mixed solution contains 0.1 to 3.0 wt% of tungsten and 0.1 to 2.0 wt% of molybdenum.
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