CN117401716A - Method for preparing tungsten trioxide from tungsten ore - Google Patents
Method for preparing tungsten trioxide from tungsten ore Download PDFInfo
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- CN117401716A CN117401716A CN202311441825.2A CN202311441825A CN117401716A CN 117401716 A CN117401716 A CN 117401716A CN 202311441825 A CN202311441825 A CN 202311441825A CN 117401716 A CN117401716 A CN 117401716A
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 132
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 48
- 239000010937 tungsten Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 25
- 239000011733 molybdenum Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000010440 gypsum Substances 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for preparing tungsten trioxide from tungsten ore includes such steps as decomposing tungsten ore with sulfuric acid and other acids, adding acid, cooling, filtering, dissolving the coarse tungstic acid to obtain solution containing tungsten, loading it in high-pressure reactor, adding tungsten trioxide powder as crystal seed, adding regulator, and thermal decomposing. Filtering and washing after decomposition is completed to obtain tungsten trioxide solid, adding a certain amount of molybdenum removing reagent into the solid tungsten trioxide powder for reaction, and filtering and washing to obtain pure tungsten trioxide powder and molybdenum solution. The yield of tungsten trioxide prepared by the method exceeds 99.5 percent, and almost all tungsten is converted into tungsten trioxide powder. The addition of seed crystals can induce and accelerate more efficient crystallization of tungsten in solution. The shape of the tungsten trioxide powder can be controlled by adding the regulator.
Description
Technical Field
The invention belongs to the field of oxide preparation, relates to a preparation method of tungsten trioxide, and in particular relates to a method for preparing tungsten trioxide from tungsten ore.
Background
Metal oxides play a critical role in the development of many advanced functional materials and smart devices. Among the metal oxides, tungsten trioxide is a relatively unique material, is an N-type semiconductor because of its versatility, has various crystal forms and has a forbidden band width of 2.5-2.8eV, and has a visible light response characteristic. Tungsten trioxide can thus be used as a light sensing device, such as a photochromic device, a transparent electrode, and the like; meanwhile, the tungsten trioxide can also be used as a visible light photocatalyst, organic pollutants and heavy metal ions in sewage are degraded by utilizing photodynamic, and the method is environment-friendly and economical; in the aspect of indoor environment detection, tungsten trioxide can be used as a gas sensor.
In order to solve the economic and environmental problems of dangerous waste alkali slag boiling, high decomposition cost, ammonia nitrogen wastewater discharge and the like in the existing alkali tungsten smelting process. Chinese patents CN201810362719.8, CN201810362594.9 and CN201810360985.7 propose a method for preparing tungsten products by decomposing tungsten ore with acid to obtain crude tungsten acid, then selectively dissolving tungsten with hydrogen peroxide, and then decomposing peroxytungstic acid solution. The technology can well solve the problems existing in the tungsten alkaline smelting, and realize the short-process direct preparation of qualified tungstic acid products. However, the product is only an intermediate tungsten product, the tungsten oxide product can be prepared by subsequent calcination treatment, and the shape and the strength are difficult to control. In addition, tungsten smelting process is mainly carried out on wolframite by traditional sodium hydroxide pressure cooking, and tungsten is leached out in the form of sodium tungstate solution. At present, sodium tungstate solution is extracted by a traditional ion exchange or extraction method to prepare ammonium tungstate solution, and APT (ammonium paratungstate) is finally prepared. The problem of ammonia nitrogen emission still cannot be avoided in this process. Meanwhile, the APT obtained by production is only a crude product in the tungsten industry. In addition, molybdenum removal from tungsten is currently performed in a liquid phase environment. Although the tungsten and molybdenum can be thoroughly separated, such as the technical proposal published in the patent CN201810362725.3 and the patent CN 201810362131.2. However, a long process is required for preparing the separated tungsten-containing solution into tungsten trioxide powder.
In order to solve the above problems, a method capable of directly preparing tungsten trioxide from tungsten solution is urgently needed in the industry at present.
Disclosure of Invention
In view of the above-mentioned shortcomings, the present invention provides a method for preparing tungsten trioxide from tungsten ore, and separating tungsten from molybdenum to produce qualified tungsten trioxide powder. The invention is realized by the following technical means:
the invention discloses a method for preparing tungsten trioxide from tungsten ore, which comprises the following steps:
(1) Mixing sulfuric acid with tungsten ore, adding acid solution for decomposition reaction, and filtering to obtain crude tungstic acid and decomposed solution;
(2) Adding sulfuric acid consumed in the step (1) into the decomposition liquid, adding gypsum accounting for 5-20% of the mass of the decomposition liquid as seed crystals, cooling and filtering to obtain gypsum and filtrate, and returning the filtrate to decompose tungsten ore;
(3) Washing the crude tungstic acid obtained in the step (1) to prepare a tungsten-containing solution;
(4) Placing the tungsten-containing solution into an autoclave, adding tungsten trioxide powder seed crystal and a regulating agent, then heating for decomposition, filtering and washing to obtain tungsten trioxide solid containing a certain amount of molybdenum trioxide;
(5) Adding a molybdenum removal reagent into tungsten trioxide solid containing a certain amount of molybdenum trioxide, heating and reacting for a period of time, and finally filtering and washing to obtain pure tungsten trioxide powder and molybdenum-containing solution.
Further, the concentration of the sulfuric acid in the step (1) is 0.2-3 mol/L;
the acid solution is selected from the group consisting of: hydrochloric acid, nitric acid or a mixed acid of both;
the liquid-solid ratio of the acid solution to the tungsten ore is 1-8:1;
the decomposition reaction temperature is 60-150 ℃ and the reaction time is 1-6 hours.
Further, the concentration of the acid solution is 0.5-10 mol/L.
Further, the concentration of the tungsten-containing solution in the step (3) is 20-1000 g/l;
the tungsten-containing solution is prepared by the following steps:
washing the crude tungstic acid obtained in the step (1), and dissolving the washed crude tungstic acid by adopting sodium hydroxide or sodium carbonate to obtain sodium metatungstate or sodium tungstate solution, or further adding a proper amount of hydrogen peroxide to obtain sodium peroxytungstate solution; or (b)
And (3) washing the crude tungstic acid obtained in the step (1), and dissolving the washed crude tungstic acid by hydrogen peroxide to obtain a peroxytungstic acid solution.
Further, the tungsten trioxide powder seed crystal of step (4) includes, but is not limited to: WO (WO) 3 ·H 2 O，WO 3 ·0.5H 2 O，WO 3 ·0.33H 2 O，WO 3 The method comprises the steps of carrying out a first treatment on the surface of the The adding amount of the tungsten trioxide powder seed crystal is WO in the solution 3 0 to 10 percent of the mass.
Further, the modulators of step (4) include, but are not limited to: sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, tartaric acid, thiourea, ethanol, ethylene glycol and propanol; the addition amount of the regulator is 0-6 mol/L.
Further, the thermal decomposition temperature in the step (4) is 120-300 ℃, and the thermal decomposition time is 0.5-24 h.
Further, the molybdenum removal reagent of step (5) includes, but is not limited to: one or a mixture of a plurality of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, hydrogen peroxide and sodium molybdate; the molar ratio of the molybdenum removal reagent to the molybdenum trioxide is 1-10:1.
Further, the reaction temperature in the step (5) is 30-100 ℃, and the reaction time is 0.5-5 h.
The invention also discloses tungsten trioxide prepared by any one of the methods.
The invention has the beneficial effects that:
the yield of tungsten trioxide prepared by the method exceeds 99.5 percent, and almost all tungsten is converted into tungsten trioxide powder. The addition of seed crystals can induce and accelerate more efficient crystallization of tungsten in solution. The shape of the tungsten trioxide powder can be controlled by adding the regulator.
Detailed Description
The invention will be further illustrated by the following examples, which are given solely for the purpose of illustration and are not to be construed as limiting the invention in any way.
Example 1
A method of preparing tungsten trioxide from tungsten ore, comprising:
(1) Mixing 1mol/L sulfuric acid with scheelite, and then adding 5mol/L hydrochloric acid to keep the liquid-solid ratio to be 6:1, controlling the reaction temperature to be 100 ℃ for 3 hours, adding sulfuric acid into filtrate obtained by filtering and washing, adding 10% of calcium sulfate, cooling and filtering, returning to decompose tungsten ore, filtering to obtain crude tungstic acid, and dissolving the crude tungstic acid by hydrogen peroxide to obtain 160g/l peroxytungstic acid solution;
(2) Then placing the peroxytungstic acid solution in an autoclave, adding tungsten trioxide powder seed crystal WO 3 And regulating agent sulfuric acid, then heating and decomposing, wherein the decomposition temperature is 200 ℃, the decomposition time is 12 hours, and the adding amount of tungsten trioxide powder seed crystal is WO in the solution 3 10% of mass; the addition amount of the regulator is 6mol/l, and the tungsten trioxide solid is obtained through filtration and washing;
(3) Adding a molybdenum removal reagent hydrogen peroxide into tungsten trioxide solid for reaction at a reaction temperature of 40 ℃ for 2 hours, wherein the molar ratio of the addition amount of the molybdenum removal reagent to molybdenum trioxide is 2:1, and finally filtering and washing to obtain pure tungsten trioxide powder and molybdenum solution;
(4) And (3) placing the tungsten trioxide solid obtained in the step (2) or the tungsten trioxide powder obtained in the step (3) in a vacuum furnace for distillation to remove molybdenum, wherein the temperature is 800 ℃, the vacuum degree is 10pa, the reaction time is 4 hours, and the pure tungsten trioxide is obtained after the reaction is finished.
Example 2
A method of preparing tungsten trioxide from tungsten ore, comprising:
(1) Mixing 0.5mol/L sulfuric acid with scheelite, and then adding 4mol/L nitric acid to keep the liquid-solid ratio as 4:1, controlling the reaction temperature to be 100 ℃ for 2 hours, adding sulfuric acid into filtrate obtained by filtering and washing, adding 20% calcium sulfate, cooling and filtering, returning to decompose tungsten ore, filtering to obtain crude tungstic acid, and dissolving the crude tungstic acid by adopting sodium hydroxide to obtain 268g/l sodium metatungstate solution;
(2) Placing sodium metatungstate solution into an autoclave, adding tungsten trioxide powder seed crystal WO 3 ·0.33H 2 O and oxalic acid as regulator, and then heating to decompose at 160 deg.c for 2 hr to obtain tungsten trioxide powder crystal seed with the amount of WO in the solution 3 5% of mass; the addition amount of the regulator is 0.5mol/L, and the tungsten trioxide solid is obtained through filtration and washing;
(3) Adding a molybdenum removal reagent hydrochloric acid into tungsten trioxide solid for reaction at the temperature of 80 ℃ for 3 hours, wherein the molar ratio of the addition amount of the molybdenum removal reagent to molybdenum trioxide is 10:1, and finally filtering and washing to obtain pure tungsten trioxide powder and molybdenum solution;
(3) And (3) placing the tungsten trioxide solid obtained in the step (2) or the tungsten trioxide powder obtained in the step (3) in a vacuum furnace for distillation and molybdenum removal, wherein the temperature is 600 ℃, the vacuum degree is 20pa, the reaction time is 6 hours, and the pure tungsten trioxide is obtained after the reaction is finished.
Example 3
A method of preparing tungsten trioxide from tungsten ore, comprising:
(1) Mixing 2mol/L sulfuric acid with scheelite, and then adding 2mol/L hydrochloric acid and 2mol/L nitric acid to keep the liquid-solid ratio as 2:1, controlling the reaction temperature to be 150 ℃ for 1 hour, adding sulfuric acid into filtrate obtained by filtering and washing, adding 5% calcium sulfate, cooling and filtering, returning to decompose tungsten ore, filtering to obtain crude tungstic acid, dissolving the crude tungstic acid by adopting sodium carbonate, and then adding hydrogen peroxide to obtain 216g/L sodium peroxytungstate solution;
(2) Placing sodium peroxodisulfate solution into an autoclave, adding tungsten trioxide powder seed crystal WO 3 ·H 2 O and modulator hydrochloric acid, then heating and decomposing, wherein the decomposing temperature is 140 ℃, the decomposing time is 6 hours, and the adding amount of tungsten trioxide powder seed crystal is WO in the solution 3 5% of mass; the addition amount of the regulator is 3mol/L, and the tungsten trioxide solid is obtained through filtration and washing;
(3) Adding a molybdenum removal reagent sodium molybdate into tungsten trioxide solid for reaction at 50 ℃ for 5 hours, wherein the molar ratio of the addition amount of the molybdenum removal reagent to molybdenum trioxide is 1:1, and finally obtaining pure tungsten trioxide powder and molybdenum solution through filtration and washing;
(4) And (3) placing the tungsten trioxide solid obtained in the step (21) or the tungsten trioxide powder obtained in the step (3) in a vacuum furnace for distillation to remove molybdenum, wherein the temperature is 800 ℃, the vacuum degree is 20pa, the reaction time is 6h, and the pure tungsten trioxide is obtained after the reaction is finished.
The present embodiments are to be considered as illustrative and not restrictive, and certain substitutions and modifications may be made on the part of the technical features of the present embodiments by those skilled in the art without creative effort, and are within the scope of the present invention.
Claims (10)
1. A method of preparing tungsten trioxide from tungsten ore, comprising:
(1) Mixing sulfuric acid with tungsten ore, adding acid solution for decomposition reaction, and filtering to obtain crude tungstic acid and decomposed solution;
(2) Adding sulfuric acid consumed in the step (1) into the decomposition liquid, adding gypsum accounting for 5-20% of the mass of the decomposition liquid as seed crystals, cooling and filtering to obtain gypsum and filtrate, and returning the filtrate to decompose tungsten ore;
(3) Washing the crude tungstic acid obtained in the step (1) to prepare a tungsten-containing solution;
(4) Placing the tungsten-containing solution into an autoclave, adding tungsten trioxide powder seed crystal and a regulating agent, then heating for decomposition, filtering and washing to obtain tungsten trioxide solid containing a certain amount of molybdenum trioxide;
(5) Adding a molybdenum removal reagent into tungsten trioxide solid containing a certain amount of molybdenum trioxide, heating and reacting for a period of time, and finally filtering and washing to obtain pure tungsten trioxide powder and molybdenum-containing solution.
2. The method according to claim 1, wherein:
the concentration of the sulfuric acid in the step (1) is 0.2-3 mol/L;
the acid solution is selected from the group consisting of: hydrochloric acid, nitric acid or a mixed acid of both;
the liquid-solid ratio of the acid solution to the tungsten ore is 1-8:1;
the decomposition reaction temperature is 60-150 ℃ and the reaction time is 1-6 hours.
3. The method according to claim 2, wherein:
the concentration of the acid solution is 0.5-10 mol/L.
4. The method according to claim 2, wherein:
the concentration of the tungsten-containing solution in the step (3) is 20-1000 g/l;
the tungsten-containing solution is prepared by the following steps:
washing the crude tungstic acid obtained in the step (1), and dissolving the washed crude tungstic acid by adopting sodium hydroxide or sodium carbonate to obtain sodium metatungstate or sodium tungstate solution, or further adding a proper amount of hydrogen peroxide to obtain sodium peroxytungstate solution; or (b)
And (3) washing the crude tungstic acid obtained in the step (1), and dissolving the washed crude tungstic acid by hydrogen peroxide to obtain a peroxytungstic acid solution.
5. The method according to claim 1, wherein:
the tungsten trioxide powder seed crystal in the step (4) comprises the following steps: WO (WO) 3 ·H 2 O，WO 3 ·0.5H 2 O，WO 3 ·0.33H 2 O，WO 3 The method comprises the steps of carrying out a first treatment on the surface of the The adding amount of the tungsten trioxide powder seed crystal is WO in the solution 3 0 to 10 percent of the mass.
6. The method according to claim 1, wherein:
the modulator of step (4) comprises: sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid, tartaric acid, thiourea, ethanol, ethylene glycol and propanol; the addition amount of the regulator is 0-6 mol/L.
7. The method according to claim 1, wherein:
the thermal decomposition temperature in the step (4) is 120-300 ℃, and the thermal decomposition time is 0.5-24 h.
8. The method according to claim 1, wherein:
the molybdenum removal reagent of step (5) comprises: one or a mixture of a plurality of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, hydrogen peroxide and sodium molybdate; the molar ratio of the molybdenum removal reagent to the molybdenum trioxide is 1-10:1.
9. The method according to claim 1, wherein:
the reaction temperature in the step (5) is 30-100 ℃, and the reaction time is 0.5-5 h.
10. Tungsten trioxide produced according to the method of any one of claims 1-9.
Priority Applications (1)
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| GB241399A (en) * | 1924-11-13 | 1925-10-22 | Koji Anjow | Process of treating a tungsten ore to obtain tungsten oxide therefrom |
| CN108559841A (en) * | 2018-04-20 | 2018-09-21 | 中南大学 | A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product |
| CN108640156A (en) * | 2018-04-20 | 2018-10-12 | 中南大学 | A method of preparing tungsten oxide and tungsten powder from scheelite |
| CN108677037A (en) * | 2018-04-20 | 2018-10-19 | 中南大学 | A kind of method that acid decomposes wolframite extraction tungsten |
| CN112899501A (en) * | 2021-01-20 | 2021-06-04 | 中南大学 | Method for treating low-grade black-white tungsten mixed ore |
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| GB241399A (en) * | 1924-11-13 | 1925-10-22 | Koji Anjow | Process of treating a tungsten ore to obtain tungsten oxide therefrom |
| CN108559841A (en) * | 2018-04-20 | 2018-09-21 | 中南大学 | A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten product |
| CN108640156A (en) * | 2018-04-20 | 2018-10-12 | 中南大学 | A method of preparing tungsten oxide and tungsten powder from scheelite |
| CN108677037A (en) * | 2018-04-20 | 2018-10-19 | 中南大学 | A kind of method that acid decomposes wolframite extraction tungsten |
| CN112899501A (en) * | 2021-01-20 | 2021-06-04 | 中南大学 | Method for treating low-grade black-white tungsten mixed ore |
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