CN116081690B - Method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag - Google Patents
Method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 237
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 239000011734 sodium Substances 0.000 title claims abstract description 85
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 85
- 239000002893 slag Substances 0.000 title claims abstract description 67
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000001556 precipitation Methods 0.000 claims abstract description 95
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 75
- 239000012535 impurity Substances 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 27
- -1 fluoride ions Chemical class 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 28
- 239000011737 fluorine Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 230000001376 precipitating effect Effects 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 229910001610 cryolite Inorganic materials 0.000 claims description 11
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010979 pH adjustment Methods 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000004131 Bayer process Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 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 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 16
- 230000002378 acidificating effect Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 127
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 27
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 22
- 229940039748 oxalate Drugs 0.000 description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 17
- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 12
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 12
- 229940039790 sodium oxalate Drugs 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 11
- 230000002411 adverse Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 235000006408 oxalic acid Nutrition 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 150000003681 vanadium Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ICCUNKAUJJAHGX-UHFFFAOYSA-D [V+5].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O Chemical compound [V+5].[V+5].[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O.[O-]P([O-])(F)=O ICCUNKAUJJAHGX-UHFFFAOYSA-D 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 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
-
- 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)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application relates to a method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag, belonging to the technical field of light metal smelting; the method comprises the following steps: dissolving vanadium slag to be treated and regulating the first pH value to obtain vanadium-containing solution; carrying out sodium removal treatment and impurity removal treatment on the vanadium-containing solution to remove sodium ions, fluoride ions, phosphate radicals and oxalate radicals in the vanadium-containing solution so as to obtain vanadium precipitation solution; carrying out acidic vanadium precipitation on the vanadium precipitation solution to obtain ammonium polyvanadate; the sodium removal treatment and the impurity removal treatment are carried out before the vanadium precipitation, so that at least part of impurity ions such as sodium ions, fluoride ions, phosphate radicals, oxalate radicals and the like are removed, the influence on the vanadium precipitation process is reduced, the vanadium precipitation rate is effectively improved, and the use amount of a vanadium precipitation agent is reduced.
Description
Technical Field
The application relates to the field of light metal smelting, in particular to a method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag.
Background
Vanadium is used as strategic metal and has important application value. Which is typically recovered as a by-product of other metal smelting processes. And bauxite is one of the vanadium-containing minerals. In the Bayer process production process, vanadium enters sodium aluminate solution and is continuously enriched, so that the decomposition rate of aluminum hydroxide is reduced and the granularity of the product is refined. The prior art aims at removing vanadium in an alumina production system, and mainly comprises three technical approaches: a mother solution precipitation method, an adsorption extraction method and a low-temperature crystallization method. The mother solution precipitation method and the adsorption extraction method are not applied to industry because of high cost and complex process flow. At present, low-temperature crystallization is widely used in industry.
The low-temperature crystallization is a method for obtaining salt precipitation slag containing vanadium by evaporating mother liquor, increasing the concentration of vanadium and caustic alkali, and then reducing the temperature of the solution to precipitate vanadate, phosphate, fluoride and the like in the solution. The treatment mode at the present stage basically utilizes vanadium slag to prepare ammonium metavanadate, and then the ammonium metavanadate is calcined into vanadium pentoxide. In the prior art, as in the Chinese patent application No. CN103159259A, a method for extracting vanadium pentoxide from the evaporation mother liquor in the process of producing alumina by Bayer process is disclosed, wherein a method for cooling and crystallizing by using the evaporation mother liquor is disclosed, and vanadium salt crystals are obtained. And further describes the process for preparing the vanadium pentoxide in detail, and the vanadium pentoxide is obtained through the technological processes of vanadium slag dissolution, calcium salt or magnesium salt impurity removal, ammonium metavanadate preparation and calcination. However, in the ammonium metavanadate preparation process, the vanadium content in the vanadium precipitation solution is high, the vanadium precipitation rate is low, and the ammonium salt consumption is large.
Disclosure of Invention
Applicants found during the course of the invention that: the Bayer process flow of alumina production is used as a wet process for treating bauxite by an alkaline method, and the sodium content in vanadium slag is high by cooling and crystallizing, wherein the Na2O content can reach 40-50%. And because vanadium in the solution is precipitated by double salt formed by vanadium fluorophosphate, the phosphorus content is as high as 6-8%, which is far more than the conventional vanadium production process. Meanwhile, organic matters in the alumina production system can be separated out along with the increase of alkalinity and the reduction of temperature, so that vanadium slag contains a certain amount of sodium oxalate, and the content of the sodium oxalate can reach 40%. Therefore, the vanadium slag obtained in the alumina process is a vanadium salt crystal with high sodium and high sodium oxalate and high impurity, and the treatment has certain difficulty. Particularly, when the [ Na2O ]/[ V2O5] mol ratio in the vanadium precipitation solution is more than 2.55, the quality of the sodium polyvanadate product is reduced, and the vanadium precipitation rate is reduced; on the other hand, the existence of organic matters can also lead to the reduction of the vanadium precipitation rate.
The application provides a method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag, which aims to solve the problem that the vanadium precipitation rate of ammonium polyvanadate prepared from vanadium slag produced by aluminum oxide production is low at present.
The embodiment of the application provides a method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag, which comprises the following steps:
dissolving vanadium slag to be treated and regulating the first pH value to obtain vanadium-containing solution;
Carrying out sodium removal treatment and impurity removal treatment on the vanadium-containing solution to remove sodium ions, fluoride ions, phosphate radicals and oxalate radicals in the vanadium-containing solution so as to obtain vanadium precipitation solution;
and carrying out acidic vanadium precipitation on the vanadium precipitation solution to obtain ammonium polyvanadate.
As an optional implementation manner, the removing sodium treatment and the impurity removing treatment are performed on the vanadium-containing solution to remove sodium ions, fluoride ions, phosphate radicals and oxalate radicals in the vanadium-containing solution, so as to obtain a vanadium precipitation solution, which specifically includes:
Performing first sodium removal treatment on the vanadium-containing solution to remove sodium ions and obtain a first sodium removal solution and cryolite;
Removing impurities from the first sodium removal liquid to remove fluoride ions, phosphate radicals and oxalate radicals, so as to obtain a primary vanadium precipitation liquid;
And performing second sodium removal treatment on the primary vanadium precipitation solution to remove sodium ions, thereby obtaining vanadium precipitation solution and sodium bicarbonate.
As an alternative embodiment, the first sodium removal agent contains aluminum ions, and the relationship between the molar content a of the aluminum ions and the molar content b of fluorine elements in the vanadium-containing solution is as follows: a: b= (1.2-1.4): 6, preparing a base material; and/or
The reaction time of the first sodium removal treatment is 40-60min.
As an alternative embodiment, the first sodium removal agent comprises aluminum chloride and/or aluminum sulfate.
As an alternative embodiment, the impurity removing agent of the impurity removing treatment contains calcium ions, and the relation between the molar content c of the calcium ions and the sum d of the molar contents of fluoride ions, phosphate radicals and oxalate radicals in the first sodium removing liquid is as follows: c: d= (1.1-1.2): 1.
As an alternative embodiment, the impurity removing agent of the impurity removing treatment comprises calcium hydroxide and/or calcium bicarbonate.
As an optional implementation manner, the second sodium removal treatment is performed on the primary product vanadium precipitation solution to remove sodium ions, so as to obtain vanadium precipitation solution and sodium bicarbonate, which specifically includes:
Introducing carbon dioxide into the primary vanadium precipitation solution to perform second sodium removal treatment so as to remove sodium ions and obtain vanadium precipitation solution and sodium bicarbonate; and/or
The temperature of the primary vanadium precipitation solution is 45-60 ℃.
As an alternative embodiment, the temperature of dissolution is 60-90 ℃; and/or
The target pH value of the first pH adjustment is 9-11; and/or
The first pH adjustment mode is to introduce carbon dioxide; and/or
The solid ratio of the vanadium-containing solution is 1.4-2.5.
As an optional implementation manner, the acidic vanadium precipitation is performed on the vanadium precipitation solution to obtain ammonium polyvanadate, which specifically includes:
Adjusting the second pH value of the vanadium precipitation solution to 6-7, adding a vanadium precipitation agent, and heating to 90-99 ℃;
Adding sulfuric acid into the vanadium precipitation solution with the temperature of 90-99 ℃ until the pH value is 2-3 for precipitating vanadium, thus obtaining ammonium polyvanadate;
Wherein the vanadium precipitating agent comprises ammonium salt, and the relation between the molar content e of the ammonium salt and the molar content f of vanadium in the vanadium precipitating liquid is as follows: e: f= (1.3-1.8): 1, a step of;
the vanadium precipitation time is 40-60min.
As an alternative embodiment, prior to the dissolving, the method further comprises: washing vanadium slag to be treated until the color of the vanadium slag to be treated is white, wherein the temperature of washing liquid for washing is 20-45 ℃.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
According to the method provided by the embodiment of the application, at least part of impurity ions such as sodium ions, fluoride ions, phosphate radicals and oxalate radicals are removed by carrying out sodium removal treatment and impurity removal treatment before vanadium precipitation, so that the influence of the impurity ions on the vanadium precipitation process is reduced, the vanadium precipitation rate is effectively improved, and the use amount of a vanadium precipitation agent is reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a flow chart of a method provided by an embodiment of the present application;
FIG. 2 is a process flow diagram of a method provided by an embodiment of the present application;
FIG. 3 is a process flow diagram of a first sodium removal treatment provided by an embodiment of the present application;
Fig. 4 is a process flow diagram of a second sodium removal treatment provided in an embodiment of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
Applicants found during the course of the invention that: the Bayer process flow of alumina production is used as a wet process for treating bauxite by an alkaline method, and the sodium content in vanadium slag is high by cooling and crystallizing, wherein the Na2O content can reach 40-50%. And because vanadium in the solution is precipitated by double salt formed by vanadium fluorophosphate, the phosphorus content is as high as 6-8%, which is far more than the conventional vanadium production process. Meanwhile, organic matters in the alumina production system can be separated out along with the increase of alkalinity and the reduction of temperature, so that vanadium slag contains a certain amount of sodium oxalate, and the content of the sodium oxalate can reach 40%. Therefore, the vanadium slag obtained in the alumina process is a vanadium salt crystal with high sodium and high sodium oxalate and high impurity, and the treatment has certain difficulty. Particularly, when the [ Na2O ]/[ V2O5] mol ratio in the vanadium precipitation solution is more than 2.55, the quality of the sodium polyvanadate product is reduced, and the vanadium precipitation rate is reduced; on the other hand, the existence of organic matters can also lead to the reduction of the vanadium precipitation rate.
As shown in fig. 1 and 2, the embodiment of the application provides a method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag, which comprises the following steps:
S0. washing vanadium slag to be treated until the color of the vanadium slag to be treated is white,
In some embodiments, the wash liquor of the wash is cold water, the cold water having a temperature of 20-45 ℃.
S1, dissolving vanadium slag to be treated and regulating the first pH value to obtain vanadium-containing solution;
In some embodiments, the temperature of dissolution is 60-90 ℃; the target pH value of the first pH adjustment is 9-11; the first pH adjustment mode is to introduce carbon dioxide; the solid ratio of the vanadium-containing solution is 1.4-2.5.
The reason for controlling the dissolution temperature to be 60-90 ℃ is to dissolve vanadium-containing slag as much as possible and maintain higher vanadium concentration, and the adverse effect of the overlarge temperature value is that the solubility of the vanadium slag is not greatly improved, and the energy consumption is high; the adverse effect of too small is that the solubility of vanadium slag is small, the concentration of vanadium is low, and the production efficiency is not beneficial to improvement.
The reason for controlling the target pH value of the first pH adjustment to be 9-11 is that under this condition, cryolite structure can be generated and subsequent impurity removal is facilitated, and too large or too small pH value is unfavorable for cryolite generation or leads to reduction of impurity removal rate.
The reason for controlling the solid ratio of the vanadium-containing solution to be 1.4-2.5 is to ensure the concentration of vanadium in the solution and improve the production efficiency, the adverse effect of the excessively large solid ratio is that the concentration of vanadium in the solution is low, the production efficiency is low, the adverse effect of the excessively small solid ratio is that the dissolution of vanadium slag is incomplete and the leaching rate of vanadium is low.
S2, carrying out sodium removal treatment and impurity removal treatment on the vanadium-containing solution to remove sodium ions, fluoride ions, phosphate radicals and oxalate radicals in the vanadium-containing solution, so as to obtain vanadium precipitation solution;
in some embodiments, the removing sodium and impurities from the vanadium-containing solution to remove sodium ions, fluoride ions, phosphate radicals and oxalate radicals in the vanadium-containing solution to obtain a vanadium precipitation solution specifically includes:
s2.1, performing first sodium removal treatment on the vanadium-containing solution to remove sodium ions, so as to obtain a first sodium removal solution and cryolite;
In some embodiments, the first sodium removal treated sodium removal agent contains aluminum ions in a molar content a relative to the molar content b of fluorine in the vanadium-containing solution that satisfies: a: b= (1.2-1.4): 6, preparing a base material; the reaction time of the first sodium removal treatment is 40-60min, and specifically, the sodium removal agent of the first sodium removal treatment can be selected from aluminum chloride and/or aluminum sulfate.
The reason for controlling the molar ratio of the aluminum element to the fluorine element in the solution to be 1.2-1.4:6 is that the cryolite structure is generated, the adverse effect of the excessive molar ratio is that the impurity aluminum element is introduced, and the adverse effect of the excessive molar ratio is that the removal rate of fluorine is lower.
S2.2, carrying out impurity removal treatment on the first sodium removal liquid to remove fluoride ions, phosphate radicals and oxalate radicals, so as to obtain a primary vanadium precipitation liquid;
In some embodiments, the impurity removing agent of the impurity removing treatment contains calcium ions, and the relationship between the molar content c of the calcium ions and the sum d of the molar contents of fluoride ions, phosphate radicals and oxalate radicals in the first sodium removing liquid is as follows: c: d= (1.1-1.2): 1. specifically, the impurity removing agent for the impurity removing treatment may be selected from calcium hydroxide and/or calcium bicarbonate.
The reason for controlling the adding amount of the impurity removing agent to be 1.1-1.2 times of the impurity amount (sum of mole amounts of phosphorus, fluorine and oxalic acid radical) is to realize the removal of the impurity, and a qualified product is obtained, wherein the adverse effect of the excessive mole ratio is that the vanadium loss rate is higher, the adverse effect of the excessive mole ratio is that the impurity removal rate is low, and the impurity content of the product is high.
S2.3, performing second sodium removal treatment on the primary vanadium precipitation solution to remove sodium ions, so as to obtain vanadium precipitation solution and sodium bicarbonate.
In some embodiments, the second sodium removal treatment is performed on the primary product vanadium precipitation solution to remove sodium ions, so as to obtain vanadium precipitation solution and sodium bicarbonate, which specifically includes:
Introducing carbon dioxide into the primary vanadium precipitation solution to perform second sodium removal treatment so as to remove sodium ions and obtain vanadium precipitation solution and sodium bicarbonate; the temperature of the primary vanadium precipitation solution is 45-60 ℃.
The reason for controlling the temperature of the primary vanadium precipitation solution to be 45-60 ℃ is that sodium bicarbonate is separated out, the adverse effect of the excessive temperature value is sodium bicarbonate decomposition, the adverse effect of the excessive temperature value is high energy consumption, and the cost is not low.
S3, carrying out acid vanadium precipitation on the vanadium precipitation liquid to obtain ammonium polyvanadate.
In some embodiments, the acid vanadium precipitation is performed on the vanadium precipitation solution to obtain ammonium polyvanadate, which specifically includes:
s3.1, performing second pH adjustment on the vanadium precipitation solution until the pH value is 6-7, adding a vanadium precipitation agent, and heating to 90-99 ℃; wherein the vanadium precipitating agent comprises ammonium salt, and the relation between the molar content e of the ammonium salt and the molar content f of vanadium in the vanadium precipitating liquid is as follows: e: f= (1.3-1.8): 1. in particular, the ammonium salt may be selected from ammonium sulphate.
S3.2, adding sulfuric acid into the vanadium precipitation solution with the temperature of 90-99 ℃ until the pH value is 2-3 to precipitate vanadium, thus obtaining ammonium polyvanadate; wherein the vanadium precipitation time is 40-60min.
By adopting the design, the vanadium extraction process in the alumina process is optimized, the influence on the vanadium precipitation process is reduced by removing the sodium and the oxalate in the system, cryolite and sodium bicarbonate are recovered, the resource utilization rate is improved, the process is optimized, the vanadium precipitation rate is improved, and the use amount of the vanadium precipitation agent is reduced.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
Taking vanadium slag precipitated from an alumina plant as an example, the water content of the salt precipitation slag is 45%, and the vanadium content is 9% (calculated on a dry basis). 70g of vanadium slag, wherein the solution is dissolved at the temperature of 80 ℃ with the liquid-solid ratio of 1.7, the concentration of vanadium in the unwashed vanadium slag solution is 30g/L, the concentration of sodium ions is 99g/L, the same amount of vanadium slag is washed by using cold water at 20 ℃, the concentration of vanadium in the washed vanadium slag solution is 26g/L, the concentration of sodium ions is 70g/L, the concentration of fluorine is 7.5g/L, and the concentration of oxalate is 5.4g/L; carbon dioxide was introduced to adjust the pH of the solution to 9. Carrying out first sodium removal treatment on the solution, adding aluminum chloride with the addition amount of [ Al: F ] in a molar ratio of 1.6:6, reacting for 40min, filtering to obtain 1.41g of solid cryolite, wherein the fluorine concentration in the first sodium removal solution is reduced to 2.21g/L, and the sodium concentration is 66.2g/L; adding calcium hydroxide into the first sodium removing solution to remove impurities, wherein the adding amount of the solution is 1.2 times the molar ratio of the solution to the impurities (phosphorus, fluorine and sodium oxalate), and the concentration of the phosphorus, fluorine and the oxalic acid in the solution after the impurities are removed is low and cannot be detected; and (3) performing second sodium removal treatment on the solution after impurity removal, cooling the solution to 45 ℃, introducing carbon dioxide gas, filtering to obtain 13.5g of solid sodium bicarbonate after no precipitation is performed, and 39.2g/L of sodium in the vanadium precipitation solution. After the sodium removal is completed, carrying out acidic vanadium precipitation, regulating the pH value of the filtrate to be 6 by using sulfuric acid, adding ammonium sulfate as a vanadium precipitating agent, wherein the use amount of the vanadium precipitating agent is 1.3 in molar ratio with vanadium, heating to 90 ℃, regulating the pH value of the solution to be about 3, reacting for 60min, filtering and washing to obtain an ammonium polyvanadate product, and the concentration of vanadium in the solution after vanadium precipitation is 0.01g/L.
Example 2
Taking vanadium slag precipitated from an alumina plant as an example, the water content of the salt precipitation slag is 45%, and the vanadium content is 9% (calculated on a dry basis). 70g of vanadium slag is dissolved at the temperature of 80 ℃ with the liquid-solid ratio of 1.4, the concentration of vanadium in unwashed vanadium slag solution is 34.5g/L, the concentration of sodium ions is 114g/L, the same amount of vanadium slag is washed by using 45 ℃ cold water, the concentration of vanadium in the washed vanadium slag solution is 29.7g/L, the concentration of sodium ions is 67g/L, the concentration of fluorine is 9.05g/L, and the concentration of oxalate is 6.8g/L; carbon dioxide was introduced to adjust the pH of the solution to 11. Carrying out first sodium removal treatment on the solution, adding aluminum sulfate with the addition amount of [ Al: F ] in a molar ratio of 1.2:6, reacting for 60min, filtering to obtain 1.40g of solid cryolite, wherein the fluorine concentration in the first sodium removal solution is reduced to 3.24g/L, and the sodium concentration is reduced to 62.7g/L; adding calcium bicarbonate into the first sodium removing solution to remove impurities, wherein the adding amount of the solution is 1.1 times of the mole ratio of the solution to the impurities (phosphorus, fluorine and sodium oxalate), and the concentration of the phosphorus, fluorine and the oxalic acid in the solution after the impurities are removed is low and cannot be detected; cooling the impurity-removed liquid to 60 ℃, introducing carbon dioxide gas, filtering to obtain 8.43g of solid sodium bicarbonate after no more sediment is precipitated, and obtaining 42.5g/L of sodium in the vanadium precipitation liquid; after the sodium removal is completed, carrying out acidic vanadium precipitation, adjusting the pH value of the solution after impurity removal to 7 by using sulfuric acid, adding ammonium sulfate as a vanadium precipitating agent, wherein the use amount of the vanadium precipitating agent is 1.6 in molar ratio with vanadium, heating to 95 ℃, adjusting the pH value of the solution to about 2.5, reacting for 60min, filtering and washing to obtain an ammonium polyvanadate product, and the concentration of vanadium in the solution after vanadium precipitation is 0.01g/L.
Example 3
Taking vanadium slag precipitated from an alumina plant as an example, the water content of the salt precipitation slag is 45%, and the vanadium content is 9% (calculated on a dry basis). 70g of vanadium slag, wherein the solution is dissolved at the temperature of 60 ℃ with the liquid-solid ratio of 2.5, the concentration of vanadium in the unwashed vanadium slag solution is 22.5g/L, the concentration of sodium ions is 74.25g/L, the same amount of vanadium slag is washed by using 45 ℃ cold water, the concentration of vanadium in the washed vanadium slag solution is 19.4g/L, the concentration of sodium ions is 61g/L, the concentration of fluorine is 5.6g/L, and the concentration of oxalate is 4.3g/L; carbon dioxide was added to adjust the pH of the solution to 9. Carrying out first sodium removal treatment on the solution, adding aluminum chloride with the addition amount of [ Al: F ] in a molar ratio of 1.2:6, reacting for 60 minutes, filtering to obtain 1.60g of solid cryolite, wherein the fluorine concentration in the first sodium removal solution is reduced to 1.14g/L, and the sodium concentration is 57.4g/L; adding calcium hydroxide into the first sodium removing solution to remove impurities, wherein the adding amount of the solution is 1.2 times the molar ratio of the solution to the impurities (phosphorus, fluorine and sodium oxalate), and the concentration of the phosphorus, fluorine and the oxalic acid in the solution after the impurities are removed is low and cannot be detected; cooling the impurity-removed liquid to 60 ℃, introducing carbon dioxide gas, filtering to obtain 10.1g of solid sodium bicarbonate after no more sediment is precipitated, and 43.4g/L of sodium in the vanadium precipitation liquid; after the sodium removal is completed, carrying out acidic vanadium precipitation, adjusting the pH value of the solution after impurity removal to be 7 by using sulfuric acid, adding ammonium sulfate as a vanadium precipitating agent, wherein the using amount of the vanadium precipitating agent is 1.8 in molar ratio with vanadium, heating to 99 ℃, adjusting the pH value of the solution to be about 2, reacting for 40min, filtering and washing to obtain an ammonium polyvanadate product, and the concentration of vanadium in the solution after vanadium precipitation is 0.01g/L.
Example 4
Taking vanadium slag precipitated from an alumina plant as an example, the water content of the salt precipitation slag is 45%, and the vanadium content is 9% (calculated on a dry basis). 70g of vanadium slag, wherein the solution is dissolved at the temperature of 85 ℃ with the liquid-solid ratio of 1.7, the concentration of vanadium in the unwashed vanadium slag solution is 30g/L, the concentration of sodium ions is 99g/L, the same amount of vanadium slag is washed by cold water at 25 ℃, the concentration of vanadium in the washed vanadium slag solution is 25g/L, the concentration of sodium ions is 67g/L, the concentration of fluorine is 6.5g/L, and the concentration of oxalate is 5.2g/L; carbon dioxide was introduced to adjust the pH of the solution to 9. Carrying out first sodium removal treatment on the solution, adding aluminum chloride with the addition amount of [ Al: F ] in a molar ratio of 1.2:6, reacting for 50min, filtering to obtain 1.32g of solid cryolite, wherein the fluorine concentration in the first sodium removal solution is reduced to 1.32g/L, and the sodium concentration is reduced to 62.5g/L; adding calcium bicarbonate into the first sodium removing solution to remove impurities, wherein the adding amount of the solution is 1.1 times of the mole ratio of the solution to the impurities (phosphorus, fluorine and sodium oxalate), and the concentration of the phosphorus, fluorine and the oxalic acid in the solution after the impurities are removed is low and cannot be detected; and (3) performing second sodium removal treatment on the impurity-removed solution after impurity removal, cooling the solution to 45 ℃, introducing carbon dioxide gas, filtering to obtain 11.8g of solid sodium bicarbonate after no precipitation is performed, and 40.6g/L of sodium in the vanadium precipitation solution. After the sodium removal is completed, carrying out acidic vanadium precipitation, regulating the pH value of the filtrate to be 6 by using sulfuric acid, adding ammonium sulfate as a vanadium precipitating agent, wherein the use amount of the vanadium precipitating agent is 1.4 in molar ratio with vanadium, heating to 90 ℃, regulating the pH value of the solution to be about 3, reacting for 60min, filtering and washing to obtain an ammonium polyvanadate product, and the concentration of vanadium in the solution after vanadium precipitation is 0.01g/L.
Comparative example 1
Taking vanadium slag precipitated from an alumina plant as an example, the water content of the salt precipitation slag is 45%, and the vanadium content is 9% (calculated on a dry basis). 70g of vanadium slag is dissolved at the temperature of 85 ℃ with the liquid-solid ratio of 1.7, the concentration of vanadium in unwashed vanadium slag solution is 30g/L, and the concentration of sodium ions is 99g/L; sulfuric acid is added to adjust the pH of the solution to 9. Adding magnesium sulfate to remove impurities, and removing phosphorus, fluorine and oxalic acid radical in the solution, wherein the addition amount is 1.2 times of the molar sum of the impurities (phosphorus, fluorine and sodium oxalate), and the concentration of the phosphorus, fluorine and oxalic acid radical in the solution after the impurities are removed is low and cannot be detected; adjusting the pH value of the solution after impurity removal to 7 by using sulfuric acid, adding ammonium sulfate as a vanadium precipitating agent, wherein the use amount of the vanadium precipitating agent is 1.8 in terms of mole ratio with vanadium, heating to 99 ℃, adjusting the pH value of the solution to about 2, reacting for 40min, filtering and washing to obtain an ammonium polyvanadate product, wherein the content of impurity sodium in the product is 8.5%, and the concentration of vanadium in the solution after vanadium precipitation is 3.2g/L.
Comparative example 2
Taking vanadium slag precipitated from an alumina plant as an example, the water content of the salt precipitation slag is 45%, and the vanadium content is 9% (calculated on a dry basis). 70g of vanadium slag is dissolved at the temperature of 85 ℃ with the liquid-solid ratio of 1.7, the concentration of vanadium in unwashed vanadium slag solution is 30g/L, and the concentration of sodium ions is 99g/L; hydrochloric acid is added for adjustment, and the pH value of the solution is adjusted to 9. Adding magnesium chloride to remove impurities, and removing phosphorus, fluorine and oxalic acid radical in the solution, wherein the addition amount is 1.2 times of the molar sum of the impurities (phosphorus, fluorine and sodium oxalate), and the concentration of the phosphorus, fluorine and oxalic acid radical in the solution after the impurities are removed is low and cannot be detected; reducing the temperature of the solution to 45 ℃, adding ammonium chloride as a vanadium precipitating agent, reacting for 40min with the vanadium precipitating agent in a molar ratio of 3.5, filtering and washing to obtain an ammonium polyvanadate product, and obtaining the ammonium metavanadate product, wherein the vanadium concentration in the solution after vanadium precipitation is 0.18g/L.
By comparison of the comparative examples and examples, it is possible to obtain: the method provided by the embodiment of the application effectively improves the vanadium precipitation rate and reduces the usage amount of the vanadium precipitation agent.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1,2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (2)
1. A method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag, which is characterized by comprising the following steps:
Dissolving vanadium slag to be treated and regulating the first pH value to obtain vanadium-containing solution, wherein the target pH value of the first pH value is 9-11; the first pH adjustment mode is to introduce carbon dioxide; the liquid-solid ratio of the vanadium-containing solution is 1.4-2.5;
Performing first sodium removal treatment on the vanadium-containing solution to remove sodium ions and obtain a first sodium removal solution and cryolite, wherein the sodium removal agent for the first sodium removal treatment contains aluminum ions, and the relation between the molar content a of the aluminum ions and the molar content b of fluorine elements in the vanadium-containing solution is as follows: a: b= (1.2-1.4): 6, preparing a base material;
the first sodium removal liquid is subjected to impurity removal treatment to remove fluoride ions, phosphate radicals and oxalate radicals, so as to obtain a primary vanadium precipitation liquid, the impurity removal agent for the impurity removal treatment contains calcium ions, and the relation between the molar content c of the calcium ions and the sum d of the molar contents of the fluoride ions, the phosphate radicals and the oxalate radicals in the first sodium removal liquid is as follows: c: d= (1.1-1.2): 1, a step of;
Introducing carbon dioxide into the primary product vanadium precipitation solution to perform a second sodium removal treatment to remove sodium ions, so as to obtain vanadium precipitation solution and sodium bicarbonate, wherein the temperature of the primary product vanadium precipitation solution is 45-60 ℃;
Adjusting the second pH value of the vanadium precipitation solution to 6-7, adding a vanadium precipitation agent, and heating to 90-99 ℃;
adding sulfuric acid into the vanadium precipitation solution at 90-99 ℃ until the pH value is 2-3 to precipitate vanadium, thus obtaining ammonium polyvanadate;
Wherein the vanadium precipitating agent comprises ammonium salt, and the relation between the molar content e of the ammonium salt and the molar content f of vanadium in the vanadium precipitating liquid is as follows: e: f= (1.3-1.8): 1, a step of; the high-sodium high-oxalate vanadium slag is vanadium slag generated in alumina production by a Bayer process, the reaction time of the first sodium removal treatment is 40-60min, the sodium removal agent of the first sodium removal treatment is selected from aluminum chloride and/or aluminum sulfate, the impurity removal agent of the impurity removal treatment is selected from calcium hydroxide and/or calcium bicarbonate, the dissolution temperature is 60-90 ℃, and the vanadium precipitation time is 40-60min.
2. The method for producing ammonium polyvanadate from high-sodium high-oxalate vanadium slag according to claim 1, wherein prior to the dissolving, the method further comprises: washing vanadium slag to be treated until the color of the vanadium slag to be treated is white, wherein the temperature of washing liquid for washing is 20-45 ℃.
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