CN108264086B - Method for preparing vanadium pentoxide by ball milling calcification-ammonification of vanadium-containing raw material - Google Patents
Method for preparing vanadium pentoxide by ball milling calcification-ammonification of vanadium-containing raw material Download PDFInfo
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- CN108264086B CN108264086B CN201810167051.1A CN201810167051A CN108264086B CN 108264086 B CN108264086 B CN 108264086B CN 201810167051 A CN201810167051 A CN 201810167051A CN 108264086 B CN108264086 B CN 108264086B
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- 238000000498 ball milling Methods 0.000 title claims abstract description 84
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 67
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002994 raw material Substances 0.000 title claims abstract description 34
- 238000004176 ammonification Methods 0.000 title claims abstract description 33
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011575 calcium Substances 0.000 claims abstract description 47
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 47
- 229960005069 Calcium Drugs 0.000 claims abstract description 44
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 40
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 37
- GFEYTWVSRDLPLE-UHFFFAOYSA-L dihydrogenvanadate Chemical compound O[V](O)([O-])=O GFEYTWVSRDLPLE-UHFFFAOYSA-L 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000926 separation method Methods 0.000 claims abstract description 28
- 239000000292 calcium oxide Substances 0.000 claims abstract description 27
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 230000002308 calcification Effects 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 229960003563 Calcium Carbonate Drugs 0.000 claims abstract description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 18
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 46
- 239000002002 slurry Substances 0.000 claims description 29
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000001099 ammonium carbonate Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- -1 aluminum chloride pentahydrate Chemical compound 0.000 claims description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H Aluminium sulfate Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- VWBLQUSTSLXQON-UHFFFAOYSA-O [NH4+].[V+5] Chemical compound [NH4+].[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-O 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BXOSZUMUQRJQOT-UHFFFAOYSA-N O.O.O.O.O.[Al] Chemical compound O.O.O.O.O.[Al] BXOSZUMUQRJQOT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 31
- 238000001914 filtration Methods 0.000 description 16
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- 235000015450 Tilia cordata Nutrition 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- 230000029087 digestion Effects 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005576 amination reaction Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000001737 promoting Effects 0.000 description 5
- CMZUMMUJMWNLFH-UHFFFAOYSA-N Sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- IHIXIJGXTJIKRB-UHFFFAOYSA-N Sodium orthovanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- MSNWSDPPULHLDL-UHFFFAOYSA-K iron(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 materials by function Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 230000001681 protective Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to a method for preparing vanadium pentoxide by ball milling calcification-ammonification of a vanadium-containing raw material, which comprises the following steps: mixing quicklime, water and a vanadium-containing raw material, then carrying out ball milling to carry out a calcification reaction, and carrying out solid-liquid separation after the reaction is finished to obtain calcium vanadate; at normal temperature, mixing the obtained calcium vanadate and ammonium salt, performing ball milling to perform an ammonification reaction, and performing solid-liquid separation after the reaction is finished to obtain a solution containing ammonium metavanadate and calcium carbonate; removing impurities from the solution containing ammonium metavanadate, cooling and crystallizing the solution after impurity removal, performing solid-liquid separation to obtain ammonium metavanadate crystals, and calcining to obtain vanadium pentoxide. According to the invention, the low liquid-solid ratio quicklime and water are mixed and ball-milling activation is combined for calcification reaction, so that the water consumption for calcification is reduced, and the calcification rate is more than 97%; meanwhile, ball milling ammonification reaction is carried out at normal temperature, so that volatilization of ammonia gas in the ammonification process is inhibited, and the ammonification rate reaches more than 98%. The invention shortens the process flow, is convenient to operate, has simple equipment and has good application prospect.
Description
Technical Field
The invention relates to the technical field of vanadium chemical metallurgy, in particular to a method for preparing vanadium pentoxide by ball milling calcification-ammonification of a vanadium-containing raw material.
Background
With the progress of science and technology, the application field of vanadium is continuously expanded, and some high-tech fields put higher requirements on the grade of vanadium raw materials, particularly vanadium oxide. At present, high-end products in the vanadium application field comprise aerospace-grade vanadium-aluminum alloy, all-vanadium redox flow battery electrolyte, nano-grade vanadium functional materials, vanadium catalysts, vanadium luminescent materials and the like. For example, in the aerospace field, vanadium-aluminum alloy is mainly used for producing jet engines, high-speed aircraft frameworks and casings of rocket engines, and the requirements on specific elements of raw material master alloys are extremely strict. In the field of all-vanadium redox flow batteries, the purity of vanadium pentoxide serving as a raw material for preparation of the all-vanadium redox flow batteries is improved as much as possible, and the energy efficiency, the working stability and the service life of an ion exchange membrane of the all-vanadium redox flow batteries can be effectively improved. In the field of vanadium catalysts, high-purity vanadium pentoxide is used as a catalyst, so that the reaction time can be greatly shortened, and the product conversion rate can be improved.
The raw materials for preparing high-purity vanadium pentoxide mainly comprise cheap and easily-obtained crude vanadium products, such as ammonium polyvanadate, sodium polyvanadate, ammonium metavanadate, 98% vanadium pentoxide, vanadium liquid and the like. The existing methods for preparing high-purity vanadium pentoxide mainly comprise a chemical precipitation purification method, an ion exchange method, a solvent extraction method, a chlorination method and the like.
CN104538660A discloses a preparation method of high-purity vanadium oxide suitable for all-vanadium redox flow batteries, which comprises the following steps: adding deionized water and sodium hydroxide into ammonium polyvanadate until the ammonium polyvanadate is completely dissolved to obtain a dissolved solution, and adding calcium oxide, calcium hydroxide or calcium hydroxide slurry into the dissolved solution until the concentration of vanadium in a liquid phase is lower than 0.1g/L to obtain calcium vanadate; adding calcium vanadate into deionized water, ammonium bicarbonate and a defoaming agent until the content of vanadium in a slag phase is lower than 1%, adding a silicon removal agent, filtering and washing to obtain calcium carbonate and a purified solution; and introducing high-purity ammonia gas into the purified solution, adjusting the pH value of the solution to 9, cooling and crystallizing until the concentration of vanadium element in the solution is lower than 2g/L, filtering to obtain high-purity ammonium metavanadate crystals, and roasting to obtain vanadium pentoxide with the purity of more than or equal to 99.5%. However, the method firstly dissolves ammonium polyvanadate, and has longer working procedures; a large amount of ammonia gas is discharged in the ammonification reaction process to generate bubbles, and defoaming agent treatment is needed.
CN103663557A discloses a method for preparing high-purity vanadium pentoxide from a vanadium-containing raw material, which comprises the steps of dissolving the vanadium-containing raw material with caustic soda, controlling the pH value of the dissolution end point to be 7-8.5, standing, filtering to remove ferric hydroxide colloid, adding hydrogen peroxide into filtrate, oxidizing, filtering, and removing colloid; and then using anion exchange resin, resolving the resin with an acid solution after the resin is saturated, adding ammonia water into the resolving solution to precipitate vanadium, producing red vanadium, filtering, washing with purified water, and roasting the red vanadium to produce high-purity vanadium pentoxide with the purity of more than 99.9%. However, the method for removing the impurities by using the anion exchange membrane has the problems of non-specific selectivity, easy adsorption of the anion impurities on the resin and pollution of the vanadium solution after the analysis.
CN105314678A discloses a preparation method of vanadium pentoxide, which comprises the following steps: a. a static mixer pipeline is used in the preheating process of the vanadium precipitation process, and the temperature of the acidic vanadium liquid is increased to 65-75 ℃ from normal temperature by utilizing steam heat exchange; b. adding the acid vanadium solution after heat exchange into an ammonium adding tank, adding ammonium sulfate, and stirring to obtain a mixed solution; c. adding the mixed solution into a precipitation tank, stirring, adjusting the pH value to 1.5-2, and heating the mixed solution to 90-boiling by steam to obtain an ammonium polyvanadate solution; d. and (3) taking the precipitate after the ammonium polyvanadate is settled, washing, drying and calcining to obtain vanadium pentoxide. However, the method has long process flow, is difficult to operate, needs heating and has high energy consumption.
CN103667710A discloses a process for cleanly producing vanadium pentoxide from high-calcium vanadium slag, which comprises the following steps: mixing the high-calcium vanadium slag with calcium salt for granulation; b. roasting; c. controlling the pH constant dilute sulfuric acid leaching; d. p, Si impurity is removed by adopting the phosphorus removing agent of the invention, and (NH) is added4)2CO3Removing impurities of Ca and Mg; e. precipitating vanadium; f. calcining to obtain powder V2O5. The method requires roasting and acid leaching steps during granulation, and increases energy consumption and environmental burden.
From the above, the problems of too long process flow, too high energy consumption, volatile acid liquid or ammonia gas used in the leaching process and the like mostly exist in the existing method for preparing high-purity vanadium pentoxide, so that a new method for preparing high-purity vanadium pentoxide needs to be developed to overcome the problems.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a method for preparing vanadium pentoxide by ball milling calcification-ammonization of a vanadium-containing raw material, which adopts low liquid-solid ratio quicklime and water mixing and ball milling activation to carry out calcification reaction, thereby omitting the step of dissolving the vanadium-containing raw material, shortening the process flow, reducing the water consumption for calcification and improving the calcification rate; the volatilization of ammonia gas is inhibited by low-temperature ball milling ammonification, so that the ammonification rate is improved; the whole process flow is simple, the operation is convenient, and the method is suitable for industrial application.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing vanadium pentoxide by ball milling calcification-ammonification of a vanadium-containing raw material, which comprises the following steps:
(1) mixing quicklime, water and a vanadium-containing raw material, then carrying out ball milling to carry out a calcification reaction, and carrying out solid-liquid separation after the reaction is finished to obtain calcium vanadate;
(2) at normal temperature, mixing the calcium vanadate obtained in the step (1) with ammonium salt, performing ball milling to perform an ammonification reaction, and performing solid-liquid separation after the reaction is completed to obtain a solution containing ammonium metavanadate and calcium carbonate;
(3) and (3) removing impurities from the solution containing ammonium metavanadate obtained in the step (2), cooling and crystallizing the solution after impurity removal, performing solid-liquid separation to obtain ammonium metavanadate crystals, and calcining to obtain vanadium pentoxide.
The vanadium-containing raw material of the present invention is a raw material commonly used in the art for preparing vanadium pentoxide, and for example, sodium orthovanadate, sodium metavanadate, sodium polyvanadate, ammonium polyvanadate, etc., but not limited thereto, and other vanadium-containing intermediate products that can be used for preparing vanadium pentoxide are also suitable for the present invention, and are not exhaustive due to space and simplicity.
According to the invention, the ratio of quicklime to water in step (1) is (3-6):1, and may be, for example, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
The unit of the liquid-solid ratio is mL/g.
According to the invention, the molar ratio of calcium in the quicklime in step (1) to vanadium in the vanadium-containing raw material is (1-1.8):1, and may be, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1 or 1.8:1, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the rotation speed of the ball milling process in the step (1) is 50-250r/min, for example, 50r/min, 80r/min, 100r/min, 120r/min, 150r/min, 180r/min, 200r/min, 230r/min or 250r/min, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the ball milling time in step (1) is 10-40min, for example, 10min, 15min, 20min, 25min, 30min, 35min or 40min, and the specific values between the above values are limited to space and for brevity, and the invention is not exhaustive.
According to the invention, the mass ratio of the total mass of the quicklime and the vanadium-containing raw material to the ball milling medium in the step (1) is 1 (3-10), and can be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, for example, and specific values between the above values are limited to space and are not exhaustive for the sake of brevity.
According to the invention, the ammonium salt in step (2) is ammonium carbonate and/or ammonium bicarbonate.
According to the invention, the molar ratio of ammonium in the ammonium salt and calcium in the calcium vanadate in step (2) is (1-1.4):1, and may be, for example, 1:1, 1.2:1, 1.3:1 or 1.4:1, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the invention, the rotation speed of the ball milling process in the step (2) is 50-250r/min, for example, 50r/min, 80r/min, 100r/min, 120r/min, 150r/min, 180r/min, 200r/min, 230r/min or 250r/min, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive.
According to the present invention, the ball milling time in the step (2) is 20-60min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, and the specific values therebetween are limited by space and for brevity, the present invention is not exhaustive.
According to the invention, the ratio of the total mass of calcium vanadate and ammonium salt to the mass of the ball milling medium in step (2) is 1 (3-8), which may be, for example, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
Adding water into the mixture slurry obtained by the ammonification reaction before the solid-liquid separation in the step (2), heating and dissolving, then carrying out the solid-liquid separation, and washing the calcium carbonate obtained by the separation.
According to the invention, the mass ratio of the water addition to the mixed slurry is (3-6):1, and may be, for example, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the invention, the heating and dissolving temperature is 80-100 ℃, and the time is 5-20 min.
According to the invention, in the step (3), an impurity removing agent is added for removing impurities, wherein the impurity removing agent is any one or a combination of at least two of aluminum sulfate, aluminum chloride or aluminum chloride pentahydrate, for example, any one of aluminum sulfate, aluminum chloride or aluminum chloride pentahydrate, and typical but non-limiting combinations are as follows: aluminum sulfate and aluminum chloride; aluminum sulfate and aluminum chloride pentahydrate; aluminum chloride and aluminum chloride pentahydrate; aluminum sulfate, aluminum chloride and aluminum chloride pentahydrate.
According to the invention, the molar ratio of aluminium in the agent for removing impurities and silicon in the solution containing ammonium metavanadate is (1-1.6):1, and may be, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1 or 1.6:1, and the specific values between the above values are not exhaustive for reasons of space and simplicity.
The calcination of ammonium metavanadate in the step (3) to prepare vanadium pentoxide is carried out by conventional operation in the field and calcination is carried out at conventional temperature in the field, and the method is not particularly limited.
The solid-liquid separation operation is carried out by the method commonly used in the field, such as filtration, suction filtration, centrifugation, sedimentation and the like, but not limited to, and other suitable methods are also suitable for the invention and are specifically selected according to the actual situation.
As a preferred technical scheme, the method for preparing vanadium pentoxide by ball milling calcification-ammonification of the vanadium-containing raw material comprises the following steps:
(1) mixing quicklime and water according to the liquid-solid ratio of (3-6) to 1, adding a vanadium-containing raw material, mixing, and then carrying out ball milling, wherein the molar ratio of calcium to vanadium is controlled to be (1-1.8) to 1, the rotating speed in the ball milling process is 50-250r/min, the time is 10-40min, the mass ratio of the total mass of the quicklime and the vanadium-containing raw material to the ball milling medium is 1 (3-10), and carrying out solid-liquid separation after the reaction is finished to obtain calcium vanadate;
(2) at normal temperature, mixing the calcium vanadate and the ammonium salt obtained in the step (1) according to the ammonium-vanadium molar ratio (1-1.4):1, carrying out ball milling for ammonification reaction, controlling the rotating speed in the ball milling process to be 50-250r/min, controlling the time to be 20-60min, controlling the mass ratio of the total mass of the calcium vanadate and the ammonium salt to the ball milling medium to be 1 (3-8), after the reaction is finished, adding water with the mass of 3-6 times of that of the obtained mixture slurry, heating to 80-100 ℃, dissolving for 5-20min, then carrying out solid-liquid separation to obtain a solution containing ammonium metavanadate and calcium carbonate, and washing the calcium carbonate obtained by separation; the ammonium salt is ammonium carbonate and/or ammonium bicarbonate;
(3) and (3) adding an impurity removing agent into the solution containing the ammonium metavanadate obtained in the step (2) for removing impurities, wherein the impurity removing agent is any one or a combination of at least two of aluminum sulfate, aluminum chloride or aluminum pentahydrate, the molar ratio of aluminum in the impurity removing agent to silicon in the solution containing the ammonium metavanadate is (1-1.6):1, cooling and crystallizing the solution after impurity removal, carrying out solid-liquid separation to obtain ammonium metavanadate crystals, and calcining to obtain vanadium pentoxide.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention carries out calcification reaction by ball milling activation, omits the step of adding alkali to dissolve the vanadium-containing raw material, and shortens the process flow.
(2) The method adopts the combination of low liquid-solid ratio quicklime and water mixing and ball milling activation, promotes the calcification reaction by using the combination of high temperature generated by lime digestion and ball milling activation, greatly reduces the water consumption for calcification, and obviously improves the calcification rate to more than 97 percent.
(3) The invention carries out ball milling ammonification reaction at lower temperature (normal temperature), thus inhibiting the volatilization of ammonia gas in the ammonification process and obviously improving the ammonification rate to more than 98 percent.
(4) The method has the advantages of simple process flow and equipment, convenient operation, easy realization of industrialization and good application prospect.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
(1) Mixing quicklime and water according to a liquid-solid ratio of 3:1, adding the mixture into a ball mill, adding sodium vanadate solid according to a molar ratio of calcium to vanadium of 1.6, controlling the ball milling rotation speed to be 100r/min, performing ball milling for 20min, wherein the mass ratio of the total mass of the quicklime and the vanadium-containing raw materials to a ball milling medium is 1:5, promoting the calcification reaction by utilizing heat generated by lime digestion and ball milling activation, filtering after the reaction is finished, and washing the obtained calcium vanadate;
(2) mixing the calcium vanadate and the ammonium carbonate obtained in the step (1) according to the ammonium-vanadium molar ratio of 1.2:1, adding the mixture into a ball mill at normal temperature for ball milling to perform ammonification reaction, controlling the ball milling rotation speed to be 80r/min, controlling the ball milling time to be 30min, and controlling the mass ratio of the calcium vanadate to the ammonium carbonate to the ball milling medium to be 1: 3;
(3) after the amination reaction is finished, adding water with the mass 6 times of that of the mixture slurry into the obtained mixture slurry, heating the mixture slurry to 90 ℃ to dissolve the mixture slurry for 10min, filtering the mixture slurry to obtain solution containing ammonium metavanadate and calcium carbonate, and washing the calcium carbonate obtained by separation;
(4) and (3) adding aluminum sulfate as an impurity removal agent into the solution containing ammonium metavanadate obtained in the step (3) according to the aluminum-silicon molar ratio of 1.3:1 for removing impurities, then cooling, crystallizing and separating to obtain ammonium metavanadate crystals, and calcining to obtain high-purity vanadium pentoxide.
Through detection, in the embodiment, the calcification rate is 98.56%, the ammonification rate is 99.32%, and the purity of the obtained vanadium pentoxide is 99.56%.
Example 2
(1) Mixing quicklime and water according to a liquid-solid ratio of 5:1, adding the mixture into a ball mill, adding ammonium polyvanadate solid according to a molar ratio of calcium to vanadium of 1.8, controlling the ball milling rotation speed to be 150r/min, performing ball milling for 40min, wherein the mass ratio of the total mass of the quicklime and the vanadium-containing raw materials to a ball milling medium is 1:8, promoting the calcification reaction by utilizing heat generated by lime digestion and ball milling activation, filtering after the reaction is finished, and washing the obtained calcium vanadate;
(2) mixing the calcium vanadate and the ammonium bicarbonate obtained in the step (1) according to the ammonium-vanadium molar ratio of 1.4:1, adding the mixture into a ball mill at normal temperature for ball milling to perform an ammonification reaction, controlling the ball milling rotation speed to be 100r/min, controlling the ball milling time to be 40min, and controlling the mass ratio of the fed material (the calcium vanadate and the ammonium bicarbonate) to the ball milling medium to be 1: 4;
(3) after the amination reaction is finished, adding water with the mass being 4 times that of the mixture slurry into the obtained mixture slurry, heating the mixture slurry to 90 ℃ to dissolve the mixture slurry for 10min, filtering the mixture slurry to obtain solution containing ammonium metavanadate and calcium carbonate, and washing the calcium carbonate obtained by separation;
(4) and (3) adding aluminum sulfate as an impurity removal agent into the solution containing ammonium metavanadate obtained in the step (3) according to the aluminum-silicon molar ratio of 1.4:1 for removing impurities, then cooling, crystallizing and separating to obtain ammonium metavanadate crystals, and calcining to obtain high-purity vanadium pentoxide.
Through detection, in the embodiment, the calcification rate is 98.92%, the ammonification rate is 99.23%, and the purity of the obtained vanadium pentoxide is 99.63%.
Example 3
(1) Mixing quicklime and water according to a liquid-solid ratio of 6:1, adding the mixture into a ball mill, adding sodium vanadate solid according to a molar ratio of calcium to vanadium of 1.3, controlling the ball milling rotation speed to be 200r/min, performing ball milling for 30min, wherein the mass ratio of the total mass of the quicklime and the vanadium-containing raw materials to a ball milling medium is 1:10, promoting the calcification reaction by utilizing heat generated by lime digestion and ball milling activation, filtering after the reaction is finished, and washing the obtained calcium vanadate;
(2) mixing the calcium vanadate and the ammonium carbonate obtained in the step (1) according to the ammonium-vanadium molar ratio of 1.2:1, adding the mixture into a ball mill at normal temperature for ball milling to perform ammonification reaction, controlling the ball milling rotation speed to be 150r/min, controlling the ball milling time to be 60min, and controlling the mass ratio of the calcium vanadate to the ammonium carbonate to the ball milling medium to be 1: 8;
(3) after the amination reaction is finished, adding water with the mass being 3 times that of the mixture slurry into the obtained mixture slurry, heating the mixture slurry to 80 ℃ for dissolving the mixture slurry for 30min, filtering the mixture slurry to obtain solution containing ammonium metavanadate and calcium carbonate, and washing the calcium carbonate obtained by separation;
(4) and (3) adding aluminum sulfate as an impurity removal agent into the solution containing ammonium metavanadate obtained in the step (3) according to the aluminum-silicon molar ratio of 1.1:1 for removing impurities, then cooling, crystallizing and separating to obtain ammonium metavanadate crystals, and calcining to obtain high-purity vanadium pentoxide.
Through detection, in the embodiment, the calcification rate is 98.76%, the ammonification rate is 98.69%, and the purity of the obtained vanadium pentoxide is 99.51%.
Example 4
(1) Mixing quicklime and water according to a liquid-solid ratio of 4:1, adding the mixture into a ball mill, adding ammonium polyvanadate solid according to a molar ratio of calcium to vanadium of 1.1, controlling the ball milling rotation speed to be 250r/min, performing ball milling for 20min, wherein the mass ratio of the total mass of the quicklime and the vanadium-containing raw materials to a ball milling medium is 1:4, promoting the calcification reaction by utilizing heat generated by lime digestion and ball milling activation, filtering after the reaction is finished, and washing the obtained calcium vanadate;
(2) mixing the calcium vanadate and the ammonium carbonate obtained in the step (1) according to the ammonium-vanadium molar ratio of 1.4:1, adding the mixture into a ball mill at normal temperature for ball milling to perform ammonification reaction, controlling the ball milling rotation speed to be 200r/min, controlling the ball milling time to be 25min, and controlling the mass ratio of the calcium vanadate to the ammonium carbonate to the ball milling medium to be 1: 6;
(3) after the amination reaction is finished, adding water with the mass 5 times of that of the mixture slurry into the obtained mixture slurry, heating the mixture slurry to 100 ℃ for dissolving for 20min, filtering the mixture slurry to obtain solution containing ammonium metavanadate and calcium carbonate, and washing the calcium carbonate obtained by separation;
(4) and (3) adding aluminum sulfate as an impurity removal agent into the solution containing ammonium metavanadate obtained in the step (3) according to the aluminum-silicon molar ratio of 1.3:1 for removing impurities, then cooling, crystallizing and separating to obtain ammonium metavanadate crystals, and calcining to obtain high-purity vanadium pentoxide.
Through detection, in the embodiment, the calcification rate is 98.12%, the ammonification rate is 99.24%, and the purity of the obtained vanadium pentoxide is 99.55%.
Example 5
(1) Mixing quicklime and water according to a liquid-solid ratio of 3:1, adding the mixture into a ball mill, adding sodium vanadate solid according to a molar ratio of calcium to vanadium of 1.0, controlling the ball milling rotation speed to be 50r/min, performing ball milling for 10min, wherein the mass ratio of the total mass of the quicklime and the vanadium-containing raw materials to a ball milling medium is 1:4, promoting the calcification reaction by utilizing heat generated by lime digestion and ball milling activation, filtering after the reaction is finished, and washing the obtained calcium vanadate;
(2) mixing the calcium vanadate and the ammonium carbonate obtained in the step (1) according to the ammonium-vanadium molar ratio of 1.0:1, adding the mixture into a ball mill at normal temperature for ball milling to perform ammonification reaction, controlling the ball milling rotation speed to be 50r/min, controlling the ball milling time to be 20min, and controlling the mass ratio of the calcium vanadate to the ammonium carbonate to the ball milling medium to be 1: 3;
(3) after the amination reaction is finished, adding water with the mass being 3 times that of the mixture slurry into the obtained mixture slurry, heating the mixture slurry to 80 ℃ for dissolving the mixture slurry for 5min, filtering the mixture slurry to obtain solution containing ammonium metavanadate and calcium carbonate, and washing the calcium carbonate obtained by separation;
(4) and (3) adding aluminum sulfate as an impurity removal agent into the solution containing ammonium metavanadate obtained in the step (3) according to the aluminum-silicon molar ratio of 1.0:1 for removing impurities, then cooling, crystallizing and separating to obtain ammonium metavanadate crystals, and calcining to obtain high-purity vanadium pentoxide.
Through detection, in the embodiment, the calcification rate is 97.38%, the ammonification rate is 98.47%, and the purity of the obtained vanadium pentoxide is 99.53%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. A method for preparing vanadium pentoxide by ball milling calcification-ammonification of a vanadium-containing raw material is characterized by comprising the following steps:
(1) mixing quicklime, water and a vanadium-containing raw material, then carrying out ball milling to carry out a calcification reaction, and carrying out solid-liquid separation after the reaction is finished to obtain calcium vanadate;
(2) at normal temperature, mixing the calcium vanadate obtained in the step (1) with ammonium salt, performing ball milling to perform an ammonification reaction, and performing solid-liquid separation after the reaction is completed to obtain a solution containing ammonium metavanadate and calcium carbonate;
(3) removing impurities from the solution containing ammonium metavanadate obtained in the step (2), cooling and crystallizing the solution after impurity removal, performing solid-liquid separation to obtain ammonium metavanadate crystals, and calcining to obtain vanadium pentoxide;
the liquid-solid ratio of the quicklime and the water in the step (1) is (3-6) to 1, and the unit of the liquid-solid ratio is mL/g;
the rotation speed of the ball milling process in the step (1) is 50-250r/min, and the time is 10-40 min;
the rotating speed of the ball milling process in the step (2) is 50-250r/min, and the time is 20-60 min.
2. The method as claimed in claim 1, wherein the molar ratio of calcium in the quicklime and vanadium in the vanadium-containing raw material in the step (1) is (1-1.8): 1.
3. The method of claim 1, wherein the mass ratio of the total mass of the quicklime and the vanadium-containing raw material to the ball milling medium in the step (1) is 1 (3-10).
4. The method of claim 1, wherein the ammonium salt of step (2) is ammonium carbonate and/or ammonium bicarbonate.
5. The method of claim 1, wherein the molar ratio of ammonium in the ammonium salt to calcium in the calcium vanadate in step (2) is (1-1.4): 1.
6. The method of claim 1, wherein the mass ratio of the total mass of the calcium vanadate and the ammonium salt to the mass of the ball milling medium in the step (2) is 1 (3-8).
7. The method according to claim 1, wherein water is added to the mixed material slurry obtained by the ammonification reaction before the solid-liquid separation in the step (2) and the mixed material slurry is dissolved by heating, then the solid-liquid separation is performed, and the separated calcium carbonate is washed.
8. The method of claim 7, wherein the mass ratio of the added water amount to the mixed slurry is (3-6): 1.
9. The method of claim 7, wherein the temperature of the heating for dissolution is 80-100 ℃ for 5-20 min.
10. The method of claim 1, wherein in the step (3), an impurity removing agent is added for removing impurities, and the impurity removing agent is any one or a combination of at least two of aluminum sulfate, aluminum chloride or aluminum chloride pentahydrate.
11. The method of claim 10, wherein the molar ratio of aluminum in the rejection agent to silicon in the solution comprising ammonium metavanadate is (1-1.6): 1.
12. The method of claim 1, wherein the method comprises the steps of:
(1) mixing quicklime and water according to the liquid-solid ratio of (3-6) to 1, adding a vanadium-containing raw material, mixing, and then carrying out ball milling, wherein the molar ratio of calcium to vanadium is controlled to be (1-1.8) to 1, the rotating speed in the ball milling process is 50-250r/min, the time is 10-40min, the mass ratio of the total mass of the quicklime and the vanadium-containing raw material to the ball milling medium is 1 (3-10), and carrying out solid-liquid separation after the reaction is finished to obtain calcium vanadate;
(2) at normal temperature, mixing the calcium vanadate and the ammonium salt obtained in the step (1) according to the ammonium-vanadium molar ratio (1-1.4):1, carrying out ball milling for ammonification reaction, controlling the rotating speed in the ball milling process to be 50-250r/min, controlling the time to be 20-60min, controlling the mass ratio of the total mass of the calcium vanadate and the ammonium salt to the ball milling medium to be 1 (3-8), after the reaction is finished, adding water with the mass of 3-6 times of that of the obtained mixture slurry, heating to 80-100 ℃, dissolving for 5-20min, then carrying out solid-liquid separation to obtain a solution containing ammonium metavanadate and calcium carbonate, and washing the calcium carbonate obtained by separation; the ammonium salt is ammonium carbonate and/or ammonium bicarbonate;
(3) and (3) adding an impurity removing agent into the solution containing the ammonium metavanadate obtained in the step (2) for removing impurities, wherein the impurity removing agent is any one or a combination of at least two of aluminum sulfate, aluminum chloride or aluminum pentahydrate, the molar ratio of aluminum in the impurity removing agent to silicon in the solution containing the ammonium metavanadate is (1-1.6):1, cooling and crystallizing the solution after impurity removal, carrying out solid-liquid separation to obtain ammonium metavanadate crystals, and calcining to obtain vanadium pentoxide.
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