CN108754186B - Method for preparing vanadium compound from vanadium-containing solution - Google Patents
Method for preparing vanadium compound from vanadium-containing solution Download PDFInfo
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- CN108754186B CN108754186B CN201810619596.1A CN201810619596A CN108754186B CN 108754186 B CN108754186 B CN 108754186B CN 201810619596 A CN201810619596 A CN 201810619596A CN 108754186 B CN108754186 B CN 108754186B
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 96
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 41
- 150000003682 vanadium compounds Chemical class 0.000 title claims abstract description 33
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 54
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 46
- 239000012535 impurity Substances 0.000 claims abstract description 43
- 238000001914 filtration Methods 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 66
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000003929 acidic solution Substances 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- -1 aluminum ions Chemical class 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) 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 3
- 230000002308 calcification Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005272 metallurgy Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910020489 SiO3 Inorganic materials 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NKSBIXNSVUBHCE-UHFFFAOYSA-N [N].[Fe].[V] Chemical compound [N].[Fe].[V] NKSBIXNSVUBHCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a vanadium compound from a vanadium-containing solution, and belongs to the technical field of chemical metallurgy. The invention solves the technical problem that the vanadium compound prepared by the existing method is easy to cause the content of aluminum to exceed the standard. The method comprises the following steps: a. adding aluminum salt into the vanadium-containing solution, adjusting the pH value to 8-12, heating and stirring, and filtering to obtain the vanadium-containing solution after impurity removal; b. adding ammonium salt into the vanadium-containing solution after impurity removal, and filtering to obtain vanadium compound precipitate; c. mixing the vanadium compound precipitate and an acid solution with the pH value of 2-6 according to a certain proportion, stirring and filtering to obtain a vanadium compound; d. and c, drying or calcining the vanadium compound in the step c to obtain ammonium metavanadate or vanadium pentoxide. The purity of the ammonium metavanadate prepared by the method is 99.7 percent, and the purity of the vanadium pentoxide is 99.9 percent. The method has the advantages of simple and convenient operation, short flow, high purity of the prepared product and good industrial prospect.
Description
Technical Field
The invention belongs to the technical field of chemical metallurgy, and particularly relates to a method for preparing a vanadium compound from a vanadium-containing solution.
Background
Vanadium is an important resource, is widely applied to various fields of national defense and economic construction due to inherent physicochemical characteristics, has excellent performance, and has wide application in industries such as metallurgy, chemical engineering and the like. The vanadium pentoxide is an important member of vanadium oxide, is widely applied in industrial production, can meet the purity requirement of vanadium-aluminum alloy on the vanadium pentoxide as a raw material in the aspect of metallurgy, and can also be used for producing vanadium-nitrogen, vanadium-iron-nitrogen and vanadium-iron alloy. In the atomic energy industry, high-purity vanadium pentoxide can be used for producing high-purity metal vanadium. In the aspect of battery industry, high-purity vanadium pentoxide can be synthesized into a positive electrode material of a lithium ion battery and a vanadium flow battery; ammonium metavanadate is mainly used as a chemical reagent, a catalyst, a drier, a mordant and the like, and is widely used as a glaze in the ceramic industry and can also be used for preparing vanadium pentoxide. Currently, commercially available ammonium metavanadate is mainly prepared by extracting, synthesizing and purifying vanadium ore, and with the wide application of vanadium pentoxide and ammonium metavanadate in various industries, people have higher and higher requirements on the purity of ammonium metavanadate, and the market prospect of high-purity ammonium metavanadate is particularly wide.
The commonly used methods for purifying vanadium pentoxide and ammonium metavanadate include chemical precipitation method for removing impurities, solvent extraction method for removing impurities and ion exchange method for removing impurities. The solvent extraction method and the ion exchange method have the main advantages that the solution with lower vanadium concentration can be enriched with vanadium through extraction or ion exchange, and vanadium products are produced after certain vanadium concentration is reached. However, the dosage of the extractant and the ion exchange resin can be increased sharply along with the increase of the concentration of the vanadium, so that the production cost of the whole vanadium product is increased, and the method is not suitable for industrial large-scale production; the chemical precipitation method is to remove the impurity elements in the vanadium by adding a precipitator, has simple process and low requirement on equipment, and is suitable for industrial large-scale production, but the impurity elements in the precipitator are easily introduced into the vanadium product in the precipitation method impurity removal process in the prior art, so that the purity of the vanadium product is difficult to improve.
At present, the requirement of the high-purity vanadium compound on the aluminum content is less than 0.005%, however, in the existing process for preparing high-purity vanadium by removing impurities with aluminum salt, the vanadium-containing solution is added with aluminum salt under the condition that the pH value is 10, the aluminum salt reacts with impurities such as Si, P and the like in the vanadium-containing solution to form precipitation and filtration, the pH value of filtrate is adjusted to 7-8 by adding sulfuric acid or hydrochloric acid to form Al (OH)3The process can obtain better silicon removal effect, but often leads to the over-standard aluminum content in the product and can not meet the production requirement of high-purity vanadium.
Disclosure of Invention
The invention aims to solve the technical problem that the content of aluminum is easy to exceed the standard in the existing preparation process for preparing vanadium pentoxide and ammonium metavanadate.
The technical scheme adopted by the invention for solving the technical problem is to provide a method for preparing a vanadium compound from a vanadium-containing solution. The method comprises the following steps:
a. adding aluminum salt into the vanadium-containing solution, adjusting the pH value to 8-12, stirring at 60-100 ℃ for 0.5-5 h, and filtering to obtain the vanadium-containing solution after impurity removal;
b. adding ammonium salt into the vanadium-containing solution after impurity removal, and filtering to obtain vanadium compound precipitate;
c. mixing an acidic solution with a pH value of 2-6 and the vanadium compound precipitate according to a liquid-solid ratio of 1-5: 1, stirring for 0.5-5 h, and filtering to obtain a vanadium compound;
d. drying or calcining the vanadium compound to obtain ammonium metavanadate or vanadium pentoxide;
the vanadium-containing solution is a leaching solution obtained by carrying out calcification roasting or blank roasting on a vanadium-containing raw material and then leaching by sodium salt.
Wherein the vanadium-containing raw material is selected from at least one of vanadium slag obtained by extracting vanadium in a converter, vanadium-containing stone coal and vanadium-containing waste catalyst.
The vanadium-containing solution contains V: 15-50 g/L, Si: 0.2-1.8 g/L, P: 0.01 to 0.4 g/L.
In the step a, the amount of the aluminum salt added is 1.1-1.5 times of the total mole amount of Si and P calculated by aluminum ions.
Wherein, in the step b, when the addition amount of the ammonium salt is NH4 +The molar ratio of the ammonium metavanadate to V is 1.1-1.5, the pH value is 9-11, and when the ammonium metavanadate reacts for 1-5 hours at room temperature, the ammonium metavanadate is obtained by filtering.
Wherein, in the step b, when the addition amount of the ammonium salt is NH4 +The molar ratio of the poly-ammonium vanadate to V is 0.3-1.0, the pH value is 2-3, and when the poly-ammonium vanadate reacts for 0.3-3 hours at the temperature of 60-95 ℃, ammonium poly-vanadate is obtained by filtering.
Wherein, in the step a, the aluminum salt is at least one selected from aluminum sulfate, aluminum nitrate and aluminum chloride.
In step c, the acidic solution is obtained by diluting at least one of sulfuric acid, nitric acid and hydrochloric acid.
In the step d, the ammonium metavanadate is dried at the temperature of 60-80 ℃ for 0.5-6 h.
In the step d, the ammonium polyvanadate is dried at the temperature of 80-100 ℃ for 0.5-3 h, and then calcined at the temperature of 500-550 ℃ for 0.5-3 h to prepare the vanadium pentoxide.
The invention has the beneficial effects that:
according to the method, the vanadium-containing solution is subjected to impurity removal by using an aluminum salt, ammonium salt is added into the vanadium-containing solution after impurity removal for vanadium precipitation, the obtained vanadium compound precipitate is washed by using an acidic solution with the pH value of 2-6 to remove aluminum ions in the vanadium-containing solution, the purity of the product is improved, the aluminum ions in the product are prevented from exceeding the standard, the purity of the prepared ammonium metavanadate can reach 99.7%, the purity of vanadium pentoxide can reach 99.9%, and the content of other impurities is less than 0.005%. Can meet the production requirement of the high-purity vanadium compound. Compared with the impurity removal by an ion exchange method or multiple precipitation impurity removal, the method has the advantages of simple and convenient process steps, short flow, low requirement on production equipment, reduced process cost, improved vanadium yield and good industrialization prospect. The method can effectively remove the cationic impurities in the vanadium pentoxide, does not introduce other impurity elements in the production process, has small pollution to the environment, and meets the requirement of environmental protection.
Detailed Description
The aluminum salt is a better reagent for removing silicon from the vanadium-containing solution, but aluminum impurity is easily introduced during silicon removal, so that the content of aluminum in the final product exceeds the standard, and the purity of the prepared product is low. Through a large amount of experimental research, the inventor finds that aluminum is AlO under alkaline conditions2 -The complex exists in a form, and the pH value is controlled to be 2-6 under an acidic condition, wherein AlO is2 -The complex of the form is first reacted with H+Generating aluminum hydroxide precipitate and further generating Al3+And further removing aluminum impurities. The purity of the ammonium metavanadate prepared by the method can reach 99.7 percent, and the purity of the vanadium pentoxide can reach 99.9 percent, so that the production requirements of high-purity ammonium metavanadate and vanadium pentoxide are met.
The invention provides a method for preparing a vanadium compound from a vanadium-containing solution. The method comprises the following steps:
a. adding aluminum salt into the vanadium-containing solution, adjusting the pH value to 8-12, stirring at 60-100 ℃ for 0.5-5 h, and filtering to obtain the vanadium-containing solution after impurity removal;
b. adding ammonium salt into the vanadium-containing solution after impurity removal, and filtering to obtain vanadium compound precipitate;
c. mixing an acidic solution with a pH value of 2-6 and the vanadium compound precipitate according to a liquid-solid ratio of 1-5: 1, stirring for 0.5-5 h, and filtering to obtain a vanadium compound;
d. drying or calcining the vanadium compound to obtain ammonium metavanadate or vanadium pentoxide;
the vanadium-containing solution is a leaching solution obtained by carrying out calcification roasting or blank roasting on a vanadium-containing raw material and then leaching by using sodium salt, wherein the vanadium-containing raw material is selected from at least one of vanadium slag obtained by extracting vanadium in a converter, vanadium-containing stone coal and vanadium-containing waste catalyst. The roasting of the vanadium-containing raw material aims to destroy the original tissue structure of vanadium, low-valence vanadium is oxidized to high-valence vanadium, and the purpose of leaching the vanadium-containing raw material by sodium salt after roasting is to dissolve out the vanadium.
The vanadium-containing solution comprises the following components: 15-50 g/L, Na: 15-50 g/L, Si: 0.2-1.8 g/L, P: 0.01-0.4 g/L, Cl <0.01g/L, Cr<0.01g/L, Fe is less than 0.01g/L, and the balance is impurities<0.01 g/L. In the step a, the amount of the aluminum salt added is 1.1-1.5 times of the total mole amount of Si and P calculated by aluminum ions. The purpose of adding the aluminum salt is to remove impurities Si and P in the vanadium-containing solution. Removing P: under the condition that the pH value is 8-12, aluminum exists in a solution in the form of a polynuclear complex, positive charges and specific surface areas generated by the complex are generally high, and the complex of the aluminum can quickly adsorb phosphate ions with negative charges in a vanadium solution; removing Si: under the condition that the pH value is 8-12, SiO3 2-With Al3+React to form Al2(SiO3)3And ↓, the temperature is controlled at 60-100 ℃, and the impurity removal efficiency is good.
Wherein, in the step a, the aluminum salt is at least one selected from aluminum sulfate, aluminum nitrate and aluminum chloride.
Wherein, in the step b, when the addition amount of the ammonium salt is NH4 +The molar ratio of the ammonium metavanadate to V is 1.1-1.5, the pH value is 9-11, and when the ammonium metavanadate reacts for 1-5 hours at room temperature, the ammonium metavanadate is obtained by filtering.
Wherein, in the step b, when the addition amount of the ammonium salt is NH4 +The molar ratio of the poly-ammonium vanadate to V is 0.3-1.0, the pH value is 2-3, and when the poly-ammonium vanadate reacts for 0.3-3 hours at the temperature of 60-95 ℃, ammonium poly-vanadate is obtained by filtering.
Wherein, in step c, the acid isThe acidic solution is a solution with a pH value of 2-6, which is obtained by diluting at least one of sulfuric acid, nitric acid and hydrochloric acid. Aluminium in AlO under alkaline condition2 -The complex in the form exists, the pH value is controlled to be 2-6, the reaction is controlled under an acidic condition, and the reaction is as follows: AlO (aluminum oxide)2 -+H++H2O＝Al(OH)3↓，Al(OH)3↓+H+＝Al3++3H2O, AlO under acidic conditions2 -The complex in its form has a high solubility, allowing it to be eluted by acid solutions.
In the step d, the ammonium metavanadate is dried at the temperature of 60-80 ℃ for 0.5-6 h.
In the step d, the ammonium polyvanadate is dried at the temperature of 80-100 ℃ for 0.5-3 h, and then calcined at the temperature of 500-550 ℃ for 0.5-3 h to prepare the vanadium pentoxide.
The present invention will be described in further detail with reference to specific examples.
The alkaline vanadium-containing solution used in the embodiment of the invention comprises the following components: v: 15-50 g/L, Na: 15-50 g/L, Si: 0.2-1.8 g/L, P: 0.01-0.4 g/L, Cl is less than 0.01g/L, Cr is less than 0.01g/L, Fe is less than 0.01g/L, and the balance is less than 0.01 g/L.
EXAMPLE 1 preparation of ammonium metavanadate in accordance with the invention
Taking 200mL of vanadium-containing solution, wherein V is 30g/L, Si is 1.2g/L, and P is 0.1g/L, adding 4.54g of Al into the vanadium-containing solution2(SO4)3·18H2Adjusting the pH value of a sodium hydroxide solution to 10, stirring for 2h at 90 ℃, filtering to obtain a vanadium-containing solution after impurity removal, adding 11.65g of ammonium sulfate into the vanadium-containing solution after impurity removal, stirring for 3h at room temperature, filtering to obtain an ammonium metavanadate precipitate, mixing a sulfuric acid solution with the pH value of 4 and the ammonium metavanadate precipitate according to the liquid-solid ratio of 3:1, stirring for 60min, filtering, and drying for 4h at 60 ℃ to obtain an ammonium metavanadate product, wherein the purity of the ammonium metavanadate is 99.7%, and the content of other impurities is less than 0.005%.
EXAMPLE 2 preparation of ammonium metavanadate in accordance with the invention
Taking 200mL of vanadium-containing solution, wherein V is 50g/L, Si is 1.8g/L,p is 0.4g/L, 3.92g Al (NO) is added to the vanadium-containing solution3)3Adjusting the pH value of a sodium hydroxide solution to 9, stirring for 3h at 80 ℃, filtering to obtain a vanadium-containing solution after impurity removal, adding 31.06g of ammonium sulfate into the vanadium-containing solution after impurity removal, stirring for 3h at room temperature, filtering to obtain an ammonium metavanadate precipitate, mixing a nitric acid solution with the pH value of 6 and the ammonium metavanadate precipitate according to the liquid-solid ratio of 2:1, stirring for 90min, filtering, and drying for 3h at 70 ℃ to obtain an ammonium metavanadate product, wherein the purity of the ammonium metavanadate is 99.6%, and the content of other impurities is less than 0.005%.
Example 3 preparation of vanadium pentoxide in the present invention
Taking 200mL of vanadium-containing solution, wherein V is 15g/L, Si is 0.2g/L, and P is 0.01g/L, adding 0.54gAl into the vanadium-containing solution2(SO4)3·18H2Adjusting the pH value of a sodium hydroxide solution to 11, stirring for 1h at 95 ℃, filtering to obtain a vanadium-containing solution after impurity removal, adjusting the pH value to 2.2 by using sulfuric acid, adding 2.33g of ammonium sulfate into the vanadium-containing solution after impurity removal, stirring for 0.5h at 95 ℃, filtering to obtain an ammonium polyvanadate precipitate, mixing the sulfuric acid solution with the pH value of 2 and the ammonium polyvanadate precipitate according to the liquid-solid ratio of 3:1, stirring for 90min, filtering, drying for 3h at 90 ℃, and calcining for 2h at 520 ℃ to obtain a vanadium pentoxide product, wherein the purity of the vanadium pentoxide is 99.8%, and the content of other impurities is less than 0.005%.
Example 4 preparation of vanadium pentoxide in the present invention
Taking 200mL of vanadium-containing solution, wherein V is 40g/L, Si is 1.50g/L, and P is 0.2g/L, adding 2.07g of AlCl into the vanadium-containing solution3Adjusting the pH value of a sodium hydroxide solution to 9, stirring for 5h at 60 ℃, filtering to obtain a vanadium-containing solution after impurity removal, adjusting the pH value to 2.0 by using sulfuric acid, adding 5.18g of ammonium sulfate into the vanadium-containing solution after impurity removal, stirring for 1h at 100 ℃, filtering to obtain an ammonium polyvanadate precipitate, mixing a hydrochloric acid solution with the pH value of 3 and the ammonium polyvanadate precipitate according to the liquid-solid ratio of 5:1, stirring for 90min, filtering, drying for 2h at 100 ℃, and calcining for 1h at 530 ℃ to obtain a vanadium pentoxide product, wherein the purity of the vanadium pentoxide is 99.9%, and the content of other impurities is less than 0.005%.
Comparative example
200mL of vanadium-containing solution is taken, wherein V is 30g/L, and Si is 1.2g/L, P0.1 g/L, adding 4.55gAl to the vanadium-containing solution2(SO4)3·18H2O, adjusting the pH value to 10 with sodium hydroxide solution, stirring for 2h at 90 ℃, filtering, adding sulfuric acid solution to adjust the pH value to 7.5, and precipitating Al (OH)3Precipitating, filtering again to obtain vanadium-containing solution after impurity removal, adding 11.65g of ammonium sulfate into the vanadium-containing solution after impurity removal, stirring for 3h at room temperature, filtering to obtain ammonium metavanadate precipitate, drying for 4h at 60 ℃ to obtain an ammonium metavanadate product, wherein the purity of the ammonium metavanadate is 99.1%, the Al content is 0.42%, and the content of other impurities is less than 0.005%.
As can be seen from the examples 1-4 and the comparative example, the purity of the ammonium metavanadate prepared by the method can reach 99.7%, and the purity of the vanadium pentoxide can reach 99.9%. The preparation method has the advantages of simple and convenient process steps, low material consumption, effective cost saving, high purity of the vanadium-containing compound prepared by the method and better industrial prospect.
Claims (7)
1. The method for preparing the vanadium compound from the vanadium-containing solution is characterized by comprising the following steps:
a. adding aluminum salt into the vanadium-containing solution, adjusting the pH value to 8-12, stirring at 60-100 ℃ for 0.5-5 h, and filtering to obtain the vanadium-containing solution after impurity removal;
b. adding ammonium salt into the vanadium-containing solution after impurity removal, and filtering to obtain vanadium compound precipitate; when the addition amount of the ammonium salt is NH4 +The molar ratio of the ammonium metavanadate to V is 1.1-1.5, the pH value is 9-11, and when the reaction is carried out for 1-5 hours at room temperature, the ammonium metavanadate is obtained by filtering; when the addition amount of the ammonium salt is NH4 +The molar ratio of the ammonium vanadate to V is 0.3-1.0, the pH value is 2-3, and when the ammonium vanadate reacts for 0.3-3 hours at the temperature of 60-95 ℃, ammonium polyvanadate is obtained by filtering;
c. mixing an acidic solution with a pH value of 2-6 and the vanadium compound precipitate according to a liquid-solid ratio of 1-5: 1, stirring for 0.5-5 h, and filtering to obtain a vanadium compound;
d. drying or calcining the vanadium compound to obtain ammonium metavanadate or vanadium pentoxide;
the vanadium-containing solution is a leaching solution obtained by carrying out calcification roasting or blank roasting on a vanadium-containing raw material and then leaching by sodium salt; the vanadium-containing solution contains V: 15-50 g/L, Si: 0.2-1.8 g/L, P: 0.01 to 0.4 g/L.
2. The method of preparing vanadium compounds according to claim 1, characterized by the fact that: the vanadium-containing raw material is selected from at least one of vanadium slag obtained by extracting vanadium in a converter, vanadium-containing stone coal and vanadium-containing waste catalyst.
3. The method for preparing vanadium compounds according to claim 1 or 2, characterized in that: in the step a, the amount of the aluminum salt added is 1.1-1.5 times of the total mole amount of Si and P calculated by aluminum ions.
4. The method of preparing vanadium compounds according to claim 1, characterized by the fact that: in step a, the aluminum salt is at least one selected from aluminum sulfate, aluminum nitrate and aluminum chloride.
5. The method of preparing vanadium compounds according to claim 1, characterized by the fact that: in step c, the acidic solution is obtained by diluting at least one of sulfuric acid, nitric acid and hydrochloric acid.
6. The method of preparing vanadium compounds according to claim 1, characterized by the fact that: in the step d, the ammonium metavanadate is dried for 0.5-6 hours at the temperature of 60-80 ℃.
7. The method of preparing vanadium compounds according to claim 1, characterized by the fact that: and drying the ammonium polyvanadate at the temperature of 80-100 ℃ for 0.5-3 h, and then calcining at the temperature of 500-550 ℃ for 0.5-3 h to prepare the vanadium pentoxide.
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| CN112266020B (en) * | 2020-11-04 | 2022-07-26 | 攀钢集团研究院有限公司 | Method for preparing vanadium pentoxide cathode material from sodium vanadium solution |
| CN113998738B (en) * | 2021-11-09 | 2023-11-10 | 攀钢集团研究院有限公司 | Method for preparing vanadium pentoxide and recycling pickling liquid using weakly alkaline vanadium liquid |
| CN113955801A (en) * | 2021-12-09 | 2022-01-21 | 淄博凡纳蒂斯技术服务有限公司 | Method for preparing high-purity ammonium metavanadate by seed crystal decomposition method |
| CN114180624B (en) * | 2021-12-23 | 2024-01-23 | 大连融科储能集团股份有限公司 | Method for preparing high-purity vanadium by separating ammonium metavanadate raw material vanadium and ammonium |
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| CN101724757B (en) * | 2009-12-31 | 2011-12-14 | 攀钢集团钢铁钒钛股份有限公司 | Method for preparing low-silicon and low-phosphorous vanadium liquid |
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