CN114243042A - Method for preparing vanadium electrolyte by circularly extracting vanadium without ammonium and liquid and vanadium electrolyte - Google Patents
Method for preparing vanadium electrolyte by circularly extracting vanadium without ammonium and liquid and vanadium electrolyte Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 153
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000003792 electrolyte Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000007788 liquid Substances 0.000 title claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 21
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003245 coal Substances 0.000 claims abstract description 3
- 239000004575 stone Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- ZMFKXOMVFFKPEC-UHFFFAOYSA-D [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZMFKXOMVFFKPEC-UHFFFAOYSA-D 0.000 claims description 2
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229940048084 pyrophosphate Drugs 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000003863 ammonium salts Chemical class 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 3
- 229940041260 vanadyl sulfate Drugs 0.000 description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- IAHBIMWHYUOIOH-UHFFFAOYSA-N vanadium hydrochloride Chemical compound Cl.[V] IAHBIMWHYUOIOH-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
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Abstract
The invention provides a method for preparing vanadium electrolyte by circularly extracting vanadium without ammonium and liquid and application thereof, wherein the method for preparing vanadium electrolyte by circularly extracting vanadium without ammonium and liquid comprises the following steps: step 1, sodium roasting; step 2, leaching and filtering; step 3, acidifying and removing impurities; step 4, reduction; step 5, extracting-back extracting vanadium; step 6, cooling and crystallizing; and 7, adjusting the valence state of the vanadium electrolyte. The vanadium-containing raw material of the invention includes but is not limited to stone coal, vanadium slag and vanadium titano-magnetite. The method for preparing the vanadium electrolyte by circularly extracting vanadium without ammonium and liquid has the advantages of short production flow, low energy consumption and no wastewater discharge, can achieve the effect of green and efficient vanadium extraction, and provides support for the aim of realizing carbon neutralization in China.
Description
Technical Field
The invention relates to a vanadium electrolyte technology, in particular to a method for preparing a vanadium electrolyte by circularly extracting vanadium from ammonium-free liquid and the vanadium electrolyte.
Background
Currently vanadium titano-magnetite is the main source of vanadium, with an original content below 1%. Through the steel-making process, iron is refined, vanadium is enriched in slag, and V2O5The content is improved to more than 8 percent, and the vanadium can be used as a source of vanadium to enter the vanadium chemical industry. The petroleum contains a small amount of vanadium, and after combustion or gasification decarburization, the vanadium is enriched, and the vanadium content in the burning ash can reach more than 5 percent.
The traditional vanadium extraction process comprises sodium salt roasting, neutralization and impurity removal, ammonium salt precipitation to obtain ammonium vanadate, high-temperature calcination or melt casting to obtain vanadium pentoxide or vanadium flakes, wherein ammonium salt is required in the process, so that a large amount of wastewater containing ammonium and sodium is generated in the vanadium extraction process, and sodium sulfate crystals are obtained by high-temperature alkali addition and deammoniation, high-temperature evaporation and drying. And a large amount of caustic soda flakes and steam are consumed during ammonium evaporation, the cost is high, the environmental pollution is serious, and a large amount of energy is consumed during evaporation and crystallization of the sodium sulfate solution.
The commercialization of the vanadium redox battery is promoted in large scale in recent years, project construction of more than 300MWH is completed at present, and according to the estimation of the energy storage alliance in the middle guan village, the project quantity of the vanadium redox battery to be built reaches 20GWH in 2024 years, and the requirement of the vanadium redox battery is about 100 cubic thousands of cubic.
The main process flow of the existing vanadium electrolyte is that raw materials with high impurity content such as ammonium metavanadate, red vanadium, ammonium polyvanadate and the like are prepared from the raw materials, then alkali is added for dissolution, impurities are removed, ammonium salt is added for vanadium precipitation, a high-purity vanadium compound is obtained, then high-temperature calcination is carried out to obtain vanadium oxide, and further the vanadium electrolyte is obtained through a dissolution-reduction mode. Obviously, the method has the disadvantages of various processes, long time consumption, huge energy consumption and huge environmental pressure. In order to meet the demand of vanadium electrolyte, a simple and low-cost electrolyte production process is urgently needed to be found.
Disclosure of Invention
The invention aims to provide a method for preparing vanadium electrolyte by extracting vanadium without ammonium and liquid circulation, aiming at the problems in the existing vanadium electrolyte production, the method has the advantages of short production flow, low energy consumption and no wastewater discharge, can achieve the effect of green and efficient vanadium extraction, and provides support for the aim of realizing carbon neutralization in China.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing vanadium electrolyte by circularly extracting vanadium without ammonium and liquid comprises the following steps:
step 1, sodium roasting
Mixing sodium carbonate and vanadium-containing raw materials (such as crushed steel slag) uniformly, putting the mixture into a kiln, and oxidizing and calcining the mixture at high temperature to convert vanadium into water-soluble sodium vanadate;
Dissolving the calcined material obtained in the step 1 in water or the crystallization mother liquor obtained in the step 6, leaching, and filtering to obtain sodium vanadate leaching solution and waste residue;
step 3, acidification and impurity removal
Adding acid to neutralize the sodium vanadate solution and precipitate out the main impurities including but not limited to silicon, aluminum and chromium; continuing adding acid for acidification;
step 4, reduction
Reducing vanadium to quadrivalence to obtain a mixed solution of quadrivalent vanadium (such as vanadyl sulfate) and sodium sulfate;
step 5, extracting-back extracting vanadium
Adding a stabilizer into the mixed solution, and carrying out liquid-liquid extraction-back extraction by using an organic phase as an extractant and acid as a back extractant to obtain an acid solution of tetravalent vanadium and a raffinate containing sodium sulfate;
step 6, cooling and crystallizing
Cooling the raffinate, stirring for crystallization, and filtering to obtain sodium sulfate crystals and crystallization mother liquor, wherein the crystallization mother liquor returns to the step 2;
step 7, adjusting the valence state of the vanadium electrolyte
Reducing the average valence state of the vanadium to the required valence state by acid dissolution (vanadyl dichloride and/or vanadyl sulfate) of the tetravalent vanadium obtained in the step 5 by using a reducing agent or an electrolysis device; the desired valence is +3 to + 4.
Further, the vanadium-containing raw material includes, but is not limited to, stone coal, vanadium slag, vanadium titano-magnetite. The vanadium-containing raw material has the granularity of less than 300 um.
Further, the mass ratio of the sodium carbonate to the vanadium in the vanadium-containing raw material in the step 1 is 1-5: 1, and the preferable mass ratio is 3-5: 1.
Further, the conditions of the high-temperature oxidation calcination in the step 1 are 700-1000 ℃, and the time is 1-24 h. The preferable conditions of the high-temperature oxidation calcination are 800-900 ℃, and the air atmosphere is 6-12 h.
Further, the liquid-solid ratio of the leaching in the step 2 is 1-10: 1, preferably, the liquid-solid ratio is 3-8: 1.
further, the acid in step 3 is a mixture of one or more of sulfuric acid, phosphoric acid and hydrochloric acid. And 3, the pH value of the acid addition end point is 1-4, and the stirring reaction time is 0.5-10 h.
Further, in the step 4, a reducing agent is reduced or added by the reduction electrolysis current, wherein the reducing agent is one or a combination of several of sulfur dioxide, glucose, sucrose, citric acid, oxalic acid, iron powder, aluminum powder, zinc powder, hydrazine hydrate and VC.
Further, the stabilizer in the step 5 is one or more of phosphoric acid, monohydrogen phosphate, dihydrogen phosphate, metaphosphate and pyrophosphate; after the stabilizer is added, the stability of the solution can be improved, and the phenomenon that the precipitation is generated to generate a third phase, which causes difficulty in separating an organic phase from a water phase, is prevented.
Further, the extractant in the step 5 is one or a mixture of more of bis (2-ethylhexyl) phosphate (P204), P507, N263 and N235. And 5, the stripping agent is one or a mixture of sulfuric acid, phosphoric acid, hydrochloric acid, pyrophosphoric acid, metaphosphoric acid, methanesulfonic acid and aminomethane sulfonic acid, and the mass ratio of the stripping agent to vanadium is 1-5: 1, preferably 3-5: 1.
Further, the cooling temperature in step 6 is <40 ℃.
Further, in the step 7, one method for reducing the average valence state of vanadium is to reduce vanadium by an electrolytic reduction method; the other is adding a reducing agent, wherein the reducing agent is glucose, citric acid, oxalic acid, sulfur dioxide and V2O3Vanadium sulfate or hydrazine hydrate.
The invention also discloses a vanadium electrolyte prepared by the method.
The invention also discloses application of the method for preparing the vanadium electrolyte by circularly extracting vanadium from the ammonium-free solution in the field of producing the vanadium electrolyte by directly extracting vanadium from the vanadium-containing raw material.
The working principle of the method for preparing the vanadium electrolyte by ammonium-free double-cycle vanadium extraction comprises the following steps:
(1) the method is ammonium-free, namely ammonium salt is not used in the vanadium extraction process, and an extraction method is used for replacing an ammonium salt precipitation method, so that the ammonium salt cost and the evaporation treatment cost of ammonium in the wastewater can be saved;
(2) the solution circulation process means that a sodium salt solution circulates in the vanadium extraction process, sodium salt is continuously enriched, sodium sulfate crystals are obtained through cooling crystallization after a certain concentration is reached, the energy consumption is obviously reduced compared with that of evaporation crystallization, and no wastewater is discharged in the vanadium extraction process; .
(3) Acidification and reduction processes, wherein main impurities in the solution are removed to obtain a purified vanadyl sulfate/sodium sulfate solution;
(4) the reduction-liquid extraction process can prepare tetravalent vanadium solution in one step, and vanadium electrolyte with qualified valence is obtained through further chemical reduction or electrolytic reduction.
Compared with the prior art, the method for preparing the vanadium electrolyte by ammonium-free double-cycle vanadium extraction and the application thereof have the following advantages:
1) the liquid-liquid extraction method is adopted to replace an ammonium salt vanadium precipitation process, so that impurity separation and vanadium purification are realized, the use of ammonium salt and subsequent ammonium removal operation are avoided, and the cost and the environmental pollution are obviously reduced;
2) the raw material leachate is directly used for extracting vanadium to prepare an acid solution of tetravalent vanadium, and the acid solution is electrolyzed to obtain electrolyte, so that the production flow of the electrolyte is greatly simplified, the cost is obviously reduced, and the time is shortened;
3) a solution circulation system is adopted, sodium is enriched in the vanadium extraction process, sodium sulfate crystals are obtained through cooling crystallization after a certain concentration is reached, the traditional evaporative crystallization process is replaced, the energy consumption can be obviously reduced, and no wastewater is discharged in the production process.
Drawings
FIG. 1 is a process flow for preparing vanadium electrolyte by circularly extracting vanadium from ammonium-free liquid;
fig. 2 is a charge-discharge cycle curve of the electrolyte.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a method for preparing vanadium electrolyte by circularly extracting vanadium from ammonium-free liquid, which comprises the following steps:
1. calcining sodium carbonate and vanadium in vanadium slag (V8.3 wt%) for 12h at 850 ℃ in an air atmosphere at the mass ratio of 1:1 to obtain a calcined product as clinker;
2. leaching the clinker with water or the crystallization mother liquor obtained in the step 6 according to the liquid-solid ratio of 4:1 to obtain vanadium slag leachate containing V31 g/L;
3. adding sulfuric acid to acidify until the pH value is 2, maintaining the temperature at 80 ℃, and continuously stirring;
4. introducing sulfur dioxide until the solution becomes pure blue;
5. adding 1g/L phosphoric acid as a stabilizer; adopting di (2-ethylhexyl) phosphate (P204) as an extracting agent, adjusting the pH value with sodium hydroxide, and extracting vanadium to an organic phase; using the mixed liquor of dilute sulfuric acid and phosphoric acid as back extractant until V2O5The concentration reaches 150 g/L;
6. cooling the raffinate to 25 ℃, crystallizing to obtain sodium sulfate crystals, and returning crystallization mother liquor to the step 2;
7. and (3) reducing the vanadium to 3.5 by using an electrolysis device to obtain the sulfur-phosphorus mixed acid vanadium electrolyte.
Compared with the traditional process for preparing the electrolyte by extracting vanadium, the water in the embodiment circulates in the system without evaporation and crystallization, the addition of ammonium sulfate and liquid caustic soda and steam required by wastewater deammoniation are avoided, and the cost saved by rough calculation is about 28000 yuan/tV2O5Reduced to 4200 yuan/m per cubic electrolyte3。
The comparison graph of the circulation efficiency of the sulfur-phosphorus mixed acid vanadium electrolyte and the reference electrolyte is shown in figure 2, wherein CE is the current efficiency, EE is the energy efficiency, and VE is the voltage efficiency; the figure shows that the performance of the sulfur-phosphorus mixed acid vanadium electrolyte has no obvious difference with the performance of the reference standard electrolyte and has excellent performance. The standard electrolyte is processed by adopting a conventional process: ammonium metavanadate raw material-impurity removal (impurity removal by complexation) -1000 degree burning to generate V2O5Processing and preparing electrolyte, wherein the electrolyte parameters are 1.6mol/L vanadium ion and 4.2mol/L sulfuric acid.
Example 2
The embodiment discloses a method for preparing vanadium electrolyte by circularly extracting vanadium from ammonium-free liquid, which comprises the following steps:
1. calcining the mixture for 6 hours at 900 ℃ in an air atmosphere with the ratio of sodium carbonate to vanadium in petroleum fly ash (V16.6 wt%) to obtain a calcined product, namely clinker;
2. leaching the clinker with water according to the liquid-solid ratio of 4:1 to obtain vanadium slag leaching liquid containing V40 g/L;
3. adding sulfuric acid to acidify until the pH value is 1.5, maintaining the temperature at 90 ℃, and continuously stirring;
4. adding 1/16 mass of citric acid according to the mass of vanadium, and continuing stirring the mixture to react until the solution becomes pure blue;
5. adding 2g/L metaphosphoric acid as a stabilizer; 2-ethylhexyl phosphate (P507) is used as an extracting agent, the pH value is adjusted by sodium hydroxide, and vanadium is extracted to an organic phase; using a mixed solution of 8mol/L hydrochloric acid and 0.1mol/L phosphoric acid as a stripping agent, and repeatedly stripping until V2O5The concentration reaches 100 g/L;
6. cooling the raffinate to 10 ℃, crystallizing to obtain sodium sulfate crystals, and returning the crystallization mother liquor to the step 2;
7. adding V2O3And adjusting the average valence of the vanadium in the stripping solution obtained in the step 5 to 3.5 to obtain the electrolyte containing vanadium hydrochloride.
Example 3
The embodiment discloses a method for preparing vanadium electrolyte by circularly extracting vanadium from ammonium-free liquid, which comprises the following steps:
1. the ratio of sodium carbonate to vanadium in petroleum gasification coke slag (V3.2%) is 5:1, air atmosphere is 700 DEG C
Calcining for 24 hours to obtain a calcined product which is clinker;
2. leaching the clinker with water according to the liquid-solid ratio of 2:1 to obtain vanadium slag leaching liquid containing V70 g/L;
3. adding sulfuric acid to acidify until the pH value is 2, maintaining the temperature at 90 ℃, and continuously stirring;
4. adding zinc powder according to the quality of vanadium, continuously stirring and reacting until the solution becomes pure blue, and filtering to remove residual zinc powder;
5. 3.5g of sodium dihydrogen phosphate is added as a stabilizer; adopting di (2-ethylhexyl) phosphate (P204) as an extracting agent, adjusting the pH value with sodium hydroxide, and extracting vanadium to an organic phase; repeatedly extracting by using methanesulfonic acid as a stripping agent until the concentration of vanadium reaches 100 g/L;
6. cooling the raffinate to 20 ℃, crystallizing to obtain sodium sulfate crystals, and returning the crystallization mother liquor to the step 2;
7. adding vanadium sulfate (V)2(SO4)3) And (4) adjusting the average valence of the vanadium in the stripping solution obtained in the step (4) to 3.5 to obtain vanadium electrolyte.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing vanadium electrolyte by circularly extracting vanadium without ammonium and liquid is characterized by comprising the following steps:
step 1, sodium roasting
Mixing sodium carbonate and vanadium-containing raw materials uniformly, putting the mixture into a kiln, and oxidizing and calcining the mixture at high temperature to convert vanadium into water-soluble sodium vanadate;
step 2, leaching and filtering
Dissolving the calcined material obtained in the step 1 in water or the crystallization mother liquor obtained in the step 6, leaching, and filtering to obtain sodium vanadate leaching solution and waste residue;
step 3, acidification and impurity removal
Adding acid to neutralize the sodium vanadate solution, removing main impurity precipitate, and continuously adding acid for acidification;
step 4, reduction
Reducing vanadium to quadrivalence to obtain a mixed solution of quadrivalent vanadium and sodium sulfate;
step 5, extracting-back extracting vanadium
Adding a stabilizer into the mixed solution, and carrying out liquid-liquid extraction-back extraction by using an organic phase as an extractant and acid as a back extractant to obtain an acid solution of tetravalent vanadium and a raffinate containing sodium sulfate;
step 6, cooling and crystallizing
Cooling the raffinate, stirring for crystallization, and filtering to obtain sodium sulfate crystals and crystallization mother liquor, wherein the crystallization mother liquor returns to the step 2;
step 7, adjusting the valence state of the vanadium electrolyte
Reducing the average valence state of the vanadium to the required valence state by acid dissolution of the tetravalent vanadium obtained in the step 5 by using a reducing agent or an electrolysis device; the desired valence is +3 to + 4.
2. The method for preparing the vanadium electrolyte by ammonium-free liquid-cycle vanadium extraction according to claim 1, wherein the vanadium-containing raw material is one or more of stone coal, vanadium slag and vanadium titano-magnetite.
3. The method for preparing the vanadium electrolyte through ammonium-free liquid circulation vanadium extraction according to claim 1, wherein the mass ratio of the sodium carbonate to the vanadium in the vanadium-containing raw material in the step 1 is 1-5: 1.
4. The method for preparing vanadium electrolyte by ammonium-free liquid-circulation vanadium extraction as claimed in claim 1, wherein the conditions of the high-temperature oxidation calcination in step 1 are 700-1000 ℃ and the time is 1-24 h.
5. The method for preparing the vanadium electrolyte by ammonium-free liquid-cycle vanadium extraction according to claim 1, wherein the acid in the step 3 is one or more of sulfuric acid, phosphoric acid and hydrochloric acid.
6. The method for preparing the vanadium electrolyte by ammonium-free liquid-cycle vanadium extraction according to claim 1, wherein the stabilizer in the step 5 is one or more of phosphoric acid, monohydrogen phosphate, dihydrogen phosphate, metaphosphate and pyrophosphate.
7. The method for preparing the vanadium electrolyte by ammonium-free liquid-cycle vanadium extraction according to claim 1, wherein the extractant in step 5 is one of bis (2-ethylhexyl) phosphate, P507, N263 and N235; the stripping agent is one or a mixture of sulfuric acid, phosphoric acid, hydrochloric acid, pyrophosphoric acid, metaphosphoric acid, methanesulfonic acid and aminomethanesulfonic acid, and the mass ratio of the stripping agent to vanadium is 1-5: 1.
8. The method for preparing vanadium electrolyte by ammonium-free liquid-circulation vanadium extraction according to claim 1, wherein the method for reducing the average valence state of vanadium in step 7 is to reduce vanadium by electrolytic reduction; the other is adding a reducing agent, wherein the reducing agent is glucose, citric acid, oxalic acid, sulfur dioxide and V2O3Vanadium sulfate or hydrazine hydrate.
9. A vanadium electrolyte, characterized by being prepared by the method of any one of claims 1 to 8.
10. The application of the method for preparing the vanadium electrolyte by circularly extracting vanadium from the ammonium-free solution according to any one of claims 1 to 8 in the field of producing the vanadium electrolyte by directly extracting vanadium from a vanadium-containing raw material.
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| CN117913335A (en) * | 2024-03-19 | 2024-04-19 | 液流储能科技有限公司 | Preparation method of vanadium-containing electrolyte, vanadium-containing electrolyte and flow battery |
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