CN111187904B - Method for decomposing scheelite - Google Patents
Method for decomposing scheelite Download PDFInfo
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- CN111187904B CN111187904B CN202010082725.5A CN202010082725A CN111187904B CN 111187904 B CN111187904 B CN 111187904B CN 202010082725 A CN202010082725 A CN 202010082725A CN 111187904 B CN111187904 B CN 111187904B
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- acid
- scheelite
- sulfuric acid
- hydrofluoric acid
- leaching
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- 238000000034 method Methods 0.000 title claims abstract description 44
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 154
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 141
- 238000002386 leaching Methods 0.000 claims abstract description 85
- 239000002253 acid Substances 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000010812 mixed waste Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 14
- 238000003723 Smelting Methods 0.000 claims description 5
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 abstract description 18
- 239000010937 tungsten Substances 0.000 abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 9
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 4
- 238000003825 pressing Methods 0.000 abstract description 4
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 5
- 238000010411 cooking Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000010009 beating Methods 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000013065 commercial product Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910003893 H2WO4 Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
-
- 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
Abstract
The invention provides a method for decomposing scheeliteBelonging to the technical field of tungsten hydrometallurgy. The method for decomposing the scheelite provided by the invention comprises the following steps of: the scheelite is decomposed by using mixed acid of sulfuric acid and hydrofluoric acid as a leaching agent. The invention adopts the mixed acid of sulfuric acid and hydrofluoric acid as a leaching agent to decompose scheelite, WO3The leaching rate is high and can reach more than 96.5 percent, compared with the acid with single component of sulfuric acid or hydrofluoric acid, the leaching agent can comprehensively exert the advantages of respective single acid, improve the decomposition rate of tungsten, avoid the problem that the tungstic acid is impure due to the fact that calcium sulfate and tungstic acid are generated by a single sulfuric acid system and leaching residues are difficult to separate, reduce the consumption of the single hydrofluoric acid for decomposing scheelite acid, and save the cost. The whole decomposition process in the method provided by the invention can be carried out under the normal pressure environment, so that the problem that the conventional main soda-lime pressing and boiling method and the sodium hydroxide pressing and boiling method need high-temperature and high-pressure decomposition conditions is solved, and the production cost is favorably reduced.
Description
Technical Field
The invention relates to the technical field of tungsten hydrometallurgy, in particular to a method for decomposing scheelite.
Background
Currently, the most industrially valuable tungsten minerals are mainly wolframite and scheelite. In the reserves of tungsten resources in China, wolframite accounts for about 20%, scheelite 70% and mixed wolframite 10%, and basically, the distribution situation of scheelite as the main tungsten mineral is formed. Because wolframite is easy to be selected and smelted, tungsten smelting enterprises mainly treat the wolframite for a long time, and with the exploitation and consumption of high-quality wolframite resources, the development and utilization of the scheelite becomes a necessary trend in order to adapt to the change of the situation of the tungsten resources.
In the prior art, the scheelite and the scheelite-wolframite mixed ore are usually decomposed by adopting a soda-beating pressure cooking method or a sodium hydroxide pressure cooking method, and although the soda-beating pressure cooking method and the soda-beating pressure cooking method are also suitable for decomposing the scheelite, the soda-beating pressure cooking method needs to be carried out under the conditions of high temperature and high pressure, so that the production cost is high. Aiming at the high-grade scheelite concentrate, the traditional process utilizes acid method decomposition, the adopted acid is mainly hydrochloric acid (HCl), the thermodynamic tendency of acid method decomposition of the scheelite concentrate is high, but tungstic acid is easily formed during hydrochloric acid decomposition to cause incomplete decomposition, and the traditional process is basically not used at present. Therefore, the economic and effective development and utilization of scheelite is a problem which needs to be solved in the field of tungsten metallurgy at present.
Disclosure of Invention
The invention aims to provide a method for decomposing scheelite, which has low production cost and WO3The leaching rate is high and can reach more than 99 percent.
In order to achieve the above object, the present invention provides the following technical solutions:
a method of decomposing scheelite, comprising the steps of:
the scheelite is decomposed by using mixed acid of sulfuric acid and hydrofluoric acid as a leaching agent.
Preferably, said scheelite WO3The grade is 50-78%.
Preferably, the molar ratio of the sulfuric acid to the hydrofluoric acid in the leaching agent is 1: 1-6.
Preferably, the total concentration of the sulfuric acid and the hydrofluoric acid in the leaching agent is 5-15 mol/L.
Preferably, the dosage ratio of the scheelite to the leaching agent is 1g: 2-5 mL.
Preferably, the leaching agent is mixed waste acid of sulfuric acid and hydrofluoric acid.
Preferably, the mixed waste acid is obtained from a fluorite-sulfuric acid method hydrofluoric acid production process or a tantalum-niobium smelting process.
Preferably, the concentration of the sulfuric acid and the hydrofluoric acid in the mixed waste acid is adjusted by adding at least one of water, concentrated sulfuric acid and concentrated hydrofluoric acid; the concentration of the concentrated sulfuric acid is more than or equal to 96 wt.%, and the concentration of the concentrated hydrofluoric acid is more than or equal to 36 wt.%.
Preferably, the temperature of the decomposition treatment is 90-100 ℃, and the time is 3-5 h.
Preferably, the decomposition treatment is carried out under stirring and heating in a water bath.
The invention provides a method for decomposing scheelite, which comprises the following steps: the scheelite is decomposed by using mixed acid of sulfuric acid and hydrofluoric acid as a leaching agent. The invention adopts the mixed acid of sulfuric acid and hydrofluoric acid as a leaching agent to decompose scheelite, WO3The leaching rate is high and can reach more than 96.5 percent, compared with the acid with single components such as sulfuric acid or hydrofluoric acid, the method can comprehensively exert the advantages of respective single acid, improve the decomposition rate of tungsten, avoid the problem that the tungstic acid is impure due to the fact that calcium sulfate and tungstic acid are generated by a single sulfuric acid system and leaching residues are difficult to separate, reduce the consumption of the single hydrofluoric acid for decomposing scheelite acid, and save the cost. The whole decomposition process in the method provided by the invention can be carried out under the normal pressure environment, so that the problem that the conventional main soda-lime pressing and boiling method and the sodium hydroxide pressing and boiling method need high-temperature and high-pressure decomposition conditions is solved, and the production cost is favorably reduced.
Furthermore, the method can adopt the mixed waste acid of sulfuric acid and hydrofluoric acid as a leaching agent to decompose scheelite, has wide source range of the mixed waste acid of sulfuric acid and hydrofluoric acid, low cost, improved additional value, comprehensive utilization of the mixed waste acid of sulfuric acid and hydrofluoric acid, waste material utilization, obvious economic benefit and provides a new idea for decomposition of scheelite and utilization of the mixed waste acid of sulfuric acid and hydrofluoric acid.
Drawings
FIG. 1 is an XRD pattern of the leaching residue obtained in examples 1 to 4 of the present invention.
Detailed Description
The invention provides a method for decomposing scheelite, which comprises the following steps:
the scheelite is decomposed by using mixed acid of sulfuric acid and hydrofluoric acid as a leaching agent.
In the present invention, WO of said scheelite3The grade is preferably 50 to 78%, more preferably 60 to 70%, and still more preferably 68.6%. The source of the scheelite in the present invention is not particularly limited, and any source known to those skilled in the art may be used. The particle size of the scheelite is not particularly limited, and the scheelite is preferably crushed and then sieved by a 250-mesh sieve, and the sieved fraction is taken out for subsequent decomposition treatment.
In the invention, the molar ratio of the sulfuric acid to the hydrofluoric acid in the leaching agent is preferably 1: 1-6, more preferably 1: 2-5, and further preferably 1: 3-5.
In the invention, the total concentration of the sulfuric acid and the hydrofluoric acid in the leaching agent is preferably 5-15 mol/L, more preferably 7-13 mol/L, and further preferably 8-12 mol/L.
In the invention, the dosage ratio of the scheelite to the leaching agent is preferably 1g: 2-5 mL, and specifically can be 1g:2mL, 1g:3mL, 1g:4mL or 1g:5 mL; in the present invention, the ratio of the scheelite to the leaching agent is preferably controlled within the above range, so that the tungsten concentration in the system is suitable and the decomposition treatment (e.g., the stirring operation) is favorably carried out.
In the invention, the leaching agent can be directly prepared from a sulfuric acid commercial product and a hydrofluoric acid commercial product according to the target concentration requirement, and can also be mixed waste acid of sulfuric acid and hydrofluoric acid generated in industrial production; in order to reduce the production cost, the invention preferably adopts mixed waste acid of sulfuric acid and hydrofluoric acid as a leaching agent.
In the invention, the mixed waste acid is preferably from a fluorite-sulfuric acid method hydrofluoric acid production process or a tantalum-niobium smelting process. The fluorite-sulfuric acid method is a main process for producing hydrofluoric acid, and hydrofluoric acid with low sulfuric acid purity (namely mixed waste acid of sulfuric acid and hydrofluoric acid) is mixed in the production process, so that the continuous purification cost is high; in the smelting process of tantalum and niobium, excessive sulfuric acid and hydrofluoric acid are adopted to decompose tantalum and niobium concentrate, and sulfuric acid is adopted for washing when the obtained decomposition liquid is extracted, separated and extracted to extract tantalum and niobium, so that a large amount of mixture of sulfuric acid and hydrofluoric acid can be generatedThe waste acid is directly treated in a waste water treatment station, which causes consumption of chemical raw materials and increase of environmental protection cost. The invention preferably adopts the mixed waste acid of sulfuric acid and hydrofluoric acid as a leaching agent for decomposing scheelite, WO3The leaching rate is more than 96.5 percent; the mixed waste acid is low in price, the production cost of decomposing scheelite by using the mixed waste acid is low, the treatment capacity of the mixed waste acid of a production enterprise is reduced, the purification cost of hydrofluoric acid or the consumption of chemical raw materials and the environmental protection cost of a tantalum-niobium production enterprise are reduced, the additional value of the mixed waste acid is improved, the mixed waste acid is comprehensively utilized, and waste is changed into valuable.
In the present invention, the concentration of sulfuric acid and hydrofluoric acid in the mixed waste acid is preferably adjusted by adding at least one of water, concentrated sulfuric acid, and concentrated hydrofluoric acid; specifically, when the concentrations of the sulfuric acid and the hydrofluoric acid in the mixed waste acid are not within the target concentration range, the sulfuric acid in the mixed waste acid can be prepared to the target concentration, or the hydrofluoric acid can be prepared to the target concentration first. In the invention, the concentration of the concentrated sulfuric acid is preferably more than or equal to 96 wt.%, more preferably 98 wt.%, the concentration of the sulfuric acid in the mixed waste acid is adjusted by the concentrated sulfuric acid, and the energy consumption of the subsequent decomposition treatment process is favorably reduced by using the property of dilution and heat release of the concentrated sulfuric acid; the concentration of concentrated hydrofluoric acid is preferably ≥ 36 wt.%, more preferably 36 wt.%. The concentrated sulfuric acid and the concentrated hydrofluoric acid in the present invention are preferably commercially available products.
In the invention, the scheelite is preferably added into the leaching agent and subjected to decomposition treatment under the conditions of stirring and water bath heating. In the present invention, the decomposition treatment is preferably carried out under normal pressure conditions; the temperature of the decomposition treatment is preferably 90-100 ℃, more preferably 95-100 ℃, and further preferably 98 ℃; the time is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, and further preferably 4 hours. The stirring speed is not specially limited, and the decomposition treatment is ensured to be smoothly carried out. In the present invention, the products formed during the decomposition treatment may have CaF as a main component2、CaSO4、H2WO2F4、H2WO3F2、H2WO4And the like.
After the decomposition treatment is completed, the present invention preferably performs solid-liquid separation on the obtained system to obtain a leaching solution and leaching residues. The solid-liquid separation method is not particularly limited, and the solid-liquid separation can be realized. In the invention, the leachate can be used for extracting tungsten after purification and impurity removal, and the leached slag can be used for purifying fluorite after washing, so that hydrofluoric acid production enterprises can recycle and produce hydrofluoric acid, and resource utilization of the leached slag is realized; the washing is preferably water washing, and the present invention is not particularly limited thereto.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, sulfuric acid having a concentration of 98 wt.% was used as a commercially available product having a density of 1.84g/mL and a substance amount concentration of 18.4 mol/L; hydrofluoric acid with the concentration of 36 wt.% is used as a commercial product, the density of the hydrofluoric acid is 1.12g/mL, and the mass concentration of the hydrofluoric acid is 20.1 mol/L; the mixed waste acid of the sulfuric acid and the hydrofluoric acid is from a certain hydrofluoric acid production enterprise.
Example 1
Measuring 100mL of water, adding the water into a beaker, slowly adding 71.7g of sulfuric acid with the concentration of 98 wt.% into the beaker under the stirring condition, and then slowly adding 143.3g of hydrofluoric acid with the concentration of 36 wt.% into the beaker to obtain a leaching agent, wherein the total concentration of the sulfuric acid and the hydrofluoric acid in the leaching agent is 10.37mol/L, and the molar ratio of the sulfuric acid to the hydrofluoric acid is 1: 3.60; weighing 100g of scheelite (250 mesh), WO3The grade is 68.6%, and the scheelite is added into a beaker; and transferring the beaker to a water bath kettle after the feeding is finished, controlling the water bath temperature at 98 ℃, and preserving the heat under the stirring condition for decomposition treatment for 4 hours.
Performing suction filtration after decomposition, washing the obtained leaching residue with water, drying, and determining the quality of the dried leaching residue and WO therein3The content and the result show that the weight of the leaching residue is 40.0g, and WO in the leaching residue3The content is 1.2 wt.%, the tungsten leaching rate is 99.3%; the XRD analysis pattern of the leaching residue is shown in figure 1, and the main component of the leaching residue is calcium fluoride according to figure 1.
Example 2
200mL of mixed waste acid of sulfuric acid and hydrofluoric acid is measured and added into a beaker, wherein the concentration of the sulfuric acid is 3.5mol/L and the concentration of the hydrofluoric acid is 5.3mol/L, 100g of hydrofluoric acid with the concentration of 36 wt.% is supplemented into the beaker under the stirring condition to obtain a leaching agent, the total concentration of the sulfuric acid and the hydrofluoric acid in the leaching agent is 12.31mol/L, and the molar ratio of the sulfuric acid to the hydrofluoric acid is 1: 4.09; weighing 100g of scheelite (250 mesh), WO3The grade is 68.6%, and the scheelite is added into a beaker; and transferring the beaker to a water bath kettle after the feeding is finished, controlling the water bath temperature at 98 ℃, and preserving the heat under the stirring condition for decomposition treatment for 4 hours.
Performing suction filtration after decomposition, washing the obtained leaching residue with water, drying, and determining the quality of the dried leaching residue and WO therein3The content and the result show that the weight of the leaching residue is 41.2g, and WO in the leaching residue3The content is 2.0 wt.%, the tungsten leaching rate is 98.8%; the XRD analysis pattern of the leaching residue is shown in figure 1, and the main component of the leaching residue is calcium fluoride according to figure 1.
Example 3
Measuring 300mL of mixed waste acid of sulfuric acid and hydrofluoric acid as a leaching agent, and adding the mixed waste acid into a beaker, wherein the concentration of the sulfuric acid is 3.5mol/L, the concentration of the hydrofluoric acid is 5.3mol/L, the total concentration of the sulfuric acid and the hydrofluoric acid in the leaching agent is 8.8mol/L, and the molar ratio of the sulfuric acid to the hydrofluoric acid is 1: 1.51; weighing 100g of scheelite (250 mesh), WO3The grade is 68.6%, and the scheelite is added into a beaker; and transferring the beaker to a water bath kettle after the feeding is finished, controlling the water bath temperature at 98 ℃, and preserving the heat under the stirring condition for decomposition treatment for 4 hours.
Is decomposed and processedFiltering, washing the obtained leaching residue with water, drying, and determining the quality of the dried leaching residue and WO therein3The content and the result show that the weight of the leaching residue is 45.7g, and WO in the leaching residue3The content is 3.0 wt.%, the tungsten leaching rate is 98.0%; the XRD analysis pattern of the leaching residue is shown in figure 1, and from figure 1, the main component of the leaching residue is calcium fluoride and contains a small amount of calcium sulfate.
Example 4
Measuring 200mL of mixed waste acid of sulfuric acid and hydrofluoric acid, adding the mixed waste acid into a beaker, wherein the concentration of the sulfuric acid is 3.5mol/L and the concentration of the hydrofluoric acid is 5.3mol/L, and adding 18g of sulfuric acid with the concentration of 98 wt.% into the beaker under the stirring condition to obtain a leaching agent, wherein the total concentration of the sulfuric acid and the hydrofluoric acid in the leaching agent is 9.25mol/L, and the molar ratio of the sulfuric acid to the hydrofluoric acid is 1: 1.20; weighing 100g of scheelite (250 mesh), WO3The grade is 68.6%, and the scheelite is added into a beaker; and transferring the beaker to a water bath kettle after the feeding is finished, controlling the water bath temperature at 98 ℃, and preserving the heat under the stirring condition for decomposition treatment for 4 hours.
Performing suction filtration after decomposition, washing the obtained leaching residue, drying, and measuring the quality of the dried leaching residue and WO therein3The content and the result show that the weight of the leaching residue is 45.8g, and WO in the leaching residue3The content is 5.5 wt.%, the tungsten leaching rate is 96.3%; the XRD analysis pattern of the leaching residue is shown in figure 1, and from figure 1, the main component of the leaching residue is calcium fluoride and contains a small amount of calcium sulfate.
Comparative example 1
Measuring 100mL of water, adding the water into a beaker, and slowly adding 198g of sulfuric acid with the concentration of 6.6mol/L into the beaker under the stirring condition; weighing 100g of scheelite (250 mesh), WO3The grade is 68.6%, and the scheelite is added into a beaker; and transferring the beaker to a water bath kettle after the feeding is finished, controlling the water bath temperature at 98 ℃, and preserving the heat under the stirring condition for decomposition treatment for 4 hours.
Performing suction filtration after decomposition, washing the obtained leaching residue, drying, and measuring the quality of the dried leaching residue and WO therein3Content, result showThe weight of the leaching residue is 94.4g, and WO in the leaching residue3The content is 70.5 wt.%, the tungsten leaching rate is 3.0 percent; indicating that tungsten almost enters leaching residues in the form of tungstic acid, and the main component of the leaching residues is tungstic acid.
As is clear from the above examples, the present invention uses a mixed acid of sulfuric acid and hydrofluoric acid as a leaching agent to decompose scheelite, WO3The leaching rate of the method is high, particularly, the mixed waste acid of sulfuric acid and hydrofluoric acid is used as a leaching agent to decompose scheelite, compared with the leaching agent prepared by using the commercial sulfuric acid product and the commercial hydrofluoric acid product, the leaching agent prepared by the method has the advantages that the leaching agent prepared by using the WO is high in WO3The leaching rate of (A) is equivalent, and WO3The leaching effect is better than that of single acid sulfuric acid; in addition, the mixed waste acid of the sulfuric acid and the hydrofluoric acid has wide source range and low cost, improves the additional value of the sulfuric acid and the hydrofluoric acid, comprehensively utilizes the waste, changes waste into valuable, has obvious economic benefit, and provides a new idea for the decomposition of the scheelite and the utilization of the mixed waste acid of the sulfuric acid and the hydrofluoric acid.
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 (4)
1. A method for decomposing scheelite, which is characterized by comprising the following steps:
decomposing the scheelite by using mixed acid of sulfuric acid and hydrofluoric acid as a leaching agent;
the leaching agent is mixed waste acid of sulfuric acid and hydrofluoric acid, the molar ratio of the sulfuric acid to the hydrofluoric acid in the leaching agent is 1: 1-6, the total concentration of the sulfuric acid and the hydrofluoric acid in the leaching agent is 5-15 mol/L, and the dosage ratio of the scheelite to the leaching agent is 1g: 2-5 mL; the mixed waste acid comes from a fluorite-sulfuric acid method hydrofluoric acid production process or a tantalum-niobium smelting process; the concentration of sulfuric acid and hydrofluoric acid in the mixed waste acid is adjusted by adding at least one of water, concentrated sulfuric acid and concentrated hydrofluoric acid; the concentration of the concentrated sulfuric acid is more than or equal to 96 wt.%, and the concentration of the concentrated hydrofluoric acid is more than or equal to 96 wt.%Concentration ≥ 36 wt.%; WO of the scheelite3The grade is 50-78%.
2. The method of claim 1, wherein the scheelite WO is3The grade is 50-78%.
3. The method according to claim 1, wherein the decomposition treatment is carried out at a temperature of 90 to 100 ℃ for 3 to 5 hours.
4. The method according to claim 1 or 3, wherein the decomposition treatment is carried out under stirring and heating in a water bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010082725.5A CN111187904B (en) | 2020-02-07 | 2020-02-07 | Method for decomposing scheelite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010082725.5A CN111187904B (en) | 2020-02-07 | 2020-02-07 | Method for decomposing scheelite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111187904A CN111187904A (en) | 2020-05-22 |
| CN111187904B true CN111187904B (en) | 2022-02-15 |
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Address after: 341000 No.62 Yingbin Avenue, Ganzhou economic and Technological Development Zone, Jiangxi Province Applicant after: Ganzhou Nonferrous Metallurgy Research Institute Co.,Ltd. Address before: 341000 No.62 Yingbin Avenue, Ganzhou economic and Technological Development Zone, Jiangxi Province Applicant before: GANZHOU NONFERROUS METALLURGICAL Research Institute |
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Application publication date: 20200522 Assignee: Ganzhou Metallurgical Research Institute Testing Technology Service Co.,Ltd. Assignor: Ganzhou Nonferrous Metallurgy Research Institute Co.,Ltd. Contract record no.: X2023980054417 Denomination of invention: A method for decomposing scheelite Granted publication date: 20220215 License type: Common License Record date: 20231227 |
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