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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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 135
- 239000010937 tungsten Substances 0.000 title claims abstract description 135
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 115
- 239000011733 molybdenum Substances 0.000 title claims abstract description 115
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000012071 phase Substances 0.000 claims abstract description 113
- 239000011259 mixed solution Substances 0.000 claims abstract description 84
- 238000000605 extraction Methods 0.000 claims abstract description 66
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 47
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 47
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 19
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008346 aqueous phase Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 56
- -1 polyoxyethylene Polymers 0.000 claims description 26
- 238000005191 phase separation Methods 0.000 claims description 24
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 16
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 12
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 29
- 239000004094 surface-active agent Substances 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 16
- 238000005272 metallurgy Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 235000015393 sodium molybdate Nutrition 0.000 description 14
- 239000011684 sodium molybdate Substances 0.000 description 14
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 238000009616 inductively coupled plasma Methods 0.000 description 13
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229920004890 Triton X-100 Polymers 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GXTVJIIYRCYTNM-UHFFFAOYSA-N [V].[Mo].[W] Chemical compound [V].[Mo].[W] GXTVJIIYRCYTNM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
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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