CN115747525A - Purification method of crude vanadium and application thereof - Google Patents
Purification method of crude vanadium and application thereof Download PDFInfo
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- CN115747525A CN115747525A CN202111599018.4A CN202111599018A CN115747525A CN 115747525 A CN115747525 A CN 115747525A CN 202111599018 A CN202111599018 A CN 202111599018A CN 115747525 A CN115747525 A CN 115747525A
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- vanadium
- ammonium
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- crude
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 148
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000000746 purification Methods 0.000 title claims abstract description 33
- 238000001556 precipitation Methods 0.000 claims abstract description 65
- 239000000706 filtrate Substances 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 29
- 239000012670 alkaline solution Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 230000001376 precipitating effect Effects 0.000 claims abstract description 23
- 239000012047 saturated solution Substances 0.000 claims abstract description 23
- 239000012065 filter cake Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 18
- 238000004090 dissolution Methods 0.000 claims abstract description 13
- 239000012492 regenerant Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 41
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 35
- 239000012535 impurity Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 20
- 230000008929 regeneration Effects 0.000 claims description 20
- 238000011069 regeneration method Methods 0.000 claims description 20
- 238000001953 recrystallisation Methods 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 150000003863 ammonium salts Chemical group 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 230000000536 complexating effect Effects 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 150000007524 organic acids Chemical group 0.000 claims description 6
- 150000005837 radical ions Chemical class 0.000 claims description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 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 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 239000001715 Ammonium malate Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 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 2
- KGECWXXIGSTYSQ-UHFFFAOYSA-N ammonium malate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)CC([O-])=O KGECWXXIGSTYSQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019292 ammonium malate Nutrition 0.000 claims description 2
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical group 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 229910001456 vanadium ion Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 silicate ions Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for purifying crude vanadium and application thereof. The purification method comprises the following steps: (1) Dissolving the crude vanadium in an alkaline solution until a saturated solution is obtained; (2) Precipitating vanadium from the saturated solution, and then separating out crystals from the saturated solution; (3) Filtering the saturated solution with the precipitated crystals to obtain a filter cake and a filtrate after vanadium precipitation, and washing the filter cake to obtain a purified vanadium-containing product; optionally, (4) adding a regenerant into the filtrate obtained after vanadium precipitation in the step (3), reacting and filtering to obtain a regenerated solution; the regenerant was used as an alkaline solution for the first step dissolution. The purification method can further recrystallize the product, and has the advantages of simple method, low cost, low equipment requirement, low energy consumption, cyclic utilization of liquid, no need of treating ammonia nitrogen wastewater, realization of closed cycle and environmental friendliness. Is suitable for large-scale industrial production and has good economic benefit.
Description
Technical Field
The invention belongs to the field of vanadium purification, and particularly relates to a method for purifying crude vanadium and application thereof.
Background
Vanadium pentoxide is widely applied to the manufacturing fields of alloy manufacture, catalysts, electrolyte for vanadium batteries and the like. At present, most vanadium products are applied to the metallurgical industry.
In order to realize low carbon emission, the use ratio of clean energy is imperative to be improved. Renewable energy sources such as wind energy, solar energy and the like are required to be provided with an electric storage and energy storage device for continuous and stable electric energy output. The large-scale electricity storage and energy storage device represented by a vanadium redox flow battery (VRB) is one of the solutions, is rapidly developed in recent years, is green and environment-friendly in manufacturing and using processes, lower in production and manufacturing cost than a fuel cell, relatively simple in production process, capable of deeply charging and discharging, capable of discharging with large current density, and has incomparable advantages of other batteries in the large-scale energy storage direction. With the development of the energy storage market and the application of the vanadium battery, the use of high-purity vanadium pentoxide in the electrolyte for the vanadium battery is bound to occupy an increasingly heavier proportion.
Numerous studies have shown that impurity ions in the electrolyte can adversely affect the vanadium battery system. For example, silicate ions reduce electrode reactivity, voltage efficiency, and energy efficiency, and accelerate the decay of battery capacity; when the concentration of calcium and magnesium ions is too high, the viscosity of the electrolyte is increased, the diffusion coefficient is reduced, the reaction speed and reversibility of the electrode are reduced, vanadium ions are precipitated, and the stability of the electrolyte is reduced; copper ions are separated out along with the oxidation-reduction process of the surface of the battery electrode and are deposited on the proton exchange membrane and the surface of the electrode, so that the stable operation of the battery is influenced; the existence of sodium, potassium and ammonium ions influences the stability of the electrolyte; the content of variable valence metal ions of iron, chromium and manganese is too high, which can generate adverse effect on the electrolyte, greatly reduce the energy efficiency and the working stability of the vanadium battery, and simultaneously reduce the service life of the ion exchange membrane. Therefore, during the preparation and use of the vanadium battery electrolyte, the introduction of impurity elements should be avoided as much as possible.
The ammonium metavanadate is a main raw material for preparing vanadium pentoxide, and in order to obtain high-purity vanadium pentoxide, high-purity ammonium metavanadate needs to be prepared firstly, so that the economic and environment-friendly preparation method is particularly important.
The method for purifying the ammonium metavanadate comprises the following steps: physical crystallization purification, chemical impurity removal purification, extraction purification, ion exchange purification, and the like, all of which have certain disadvantages.
A crystallization method: when the crystallization method is used alone, the liquid-solid ratio is high, the energy consumption is high, the temperature rise and the temperature decrease are realized, the crystallization time is long, and the crystals are stained on the wall. The impurity elements in the crystallized solution accumulate and need to be treated again.
The chemical method comprises the following steps: the process is relatively complex, the pH value needs to be adjusted for multiple times, impurities can be introduced by an external medicament, the cost of the high-purity medicament is high, high-salt and high-ammonia nitrogen wastewater needs to be treated, and the vanadium loss is large.
Extraction method: the production process is complicated by the processes of multi-stage extraction, back extraction and the like, the production period is long, and a third phase is easily generated in the extraction process, so that the extraction is ineffective. The extractant is organic matter, generally has certain toxicity, also needs to treat vanadium precipitation waste water.
Ion exchange method: the operation is complex, a large amount of waste water is generated during resin desorption and regeneration, the production period is long, and the production capacity is small due to the limitation of adsorption capacity. Meanwhile, a small amount of impurity ions and active functional groups are replaced in the ion exchange process, so that the purpose of complete purification cannot be achieved. The ion exchange elements are more, different exchange columns are needed, and the water treatment amount is large. In addition, a part of vanadium is still not crystallized out in the original solution, and the loss of vanadium is possibly increased.
No matter which method is used, when ammonium salt (such as ammonium sulfate, ammonium chloride and the like) is finally used for precipitating vanadium, a problem is necessarily caused, namely the problem of treating high ammonia nitrogen and high salt wastewater is the problem which is recognized as a difficult point and a key point; and is also the bottleneck for purifying ammonium metavanadate. High ammonia nitrogen and high salt wastewater treatment difficulty is high, pollution problems are prominent, and large-scale industrial application of the wastewater is severely restricted. The traditional treatment method needs evaporative crystallization, and has high energy consumption, long flow path and high investment.
Disclosure of Invention
In order to solve the problems, the invention provides a method for purifying crude vanadium and application thereof.
In order to achieve the above object, the present invention provides a method for purifying crude vanadium, comprising the steps of:
(1) Dissolving crude vanadium in an alkaline solution until a saturated solution is obtained;
(2) After the saturated solution is subjected to vanadium precipitation treatment, crystals are separated out from the saturated solution;
(3) Filtering the saturated solution with the precipitated crystals to obtain a filter cake and a filtrate after vanadium precipitation, and washing the filter cake to obtain a purified vanadium-containing product; optionally, the first and second coating layers are formed by coating,
(4) Adding a regenerant into the filtrate obtained after vanadium precipitation in the step (3), reacting and filtering to obtain a regenerated solution; and (2) using the regeneration liquid as an alkaline solution for dissolving crude vanadium in the step (1).
According to an embodiment of the invention, the crude vanadium is selected from at least one of ammonium metavanadate, ammonium polyvanadate, sodium polyvanadate and vanadium pentoxide containing impurities.
Preferably, the impurities are selected from at least one of Al, ca, co, cr, cu, fe, K, mg, mn, mo, na, si.
Preferably, the impurity content in the crude vanadium is 0.1 to 0wt%, preferably 0.5 to 5wt%.
Preferably, the vanadium in the crude vanadium comprises low vanadium, the low vanadium accounting for 0.1-10 wt%, preferably 0.5-5 wt% of the total amount of vanadium.
The low-valence vanadium in the present invention means that at least one of the following forms of vanadium ion is present in the crude vanadium: v +2 、V +3 、V +4 。
According to an embodiment of the invention, the dissolution is carried out under stirring. Preferably, the stirring speed is 100 to 1000r/min, preferably 300 to 500r/min.
According to an embodiment of the present invention, the present invention does not limit the temperature of the dissolution in the step (1) as long as the dissolution can be achieved. The temperature of the dissolution is illustratively 10 to 95 deg.C, preferably 30 to 50 deg.C, for example 30 deg.C.
According to an embodiment of the invention, the time of dissolution is 1 to 120min, preferably 30 to 60min.
According to an embodiment of the present invention, the alkaline solution is selected from a mixed solution of ammonia and alkali.
Preferably, the base is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
According to an embodiment of the present invention, the mass percentage of ammonia in the alkaline solution is 0 to 25%, preferably 1 to 5%, and more preferably 1.5 to 3%, respectively.
According to an embodiment of the present invention, the alkali in the alkaline solution has a mass fraction of 0 to 15%, preferably 2 to 7.5%, and more preferably 2 to 5%.
According to an embodiment of the invention, the ratio of the mass of the crude vanadium to the total mass of ammonia and base in the alkaline solution is between 2 and 5.
According to an embodiment of the present invention, the saturated solution may also be subjected to impurity removal. Preferably, the impurity removal comprises preliminary filtration after adding a precipitating agent into the saturated solution to remove part of the impurities. Preferably, after the preliminary filtration, a residue and a saturated solution after filtration are obtained.
Preferably, the precipitating agent is selected from the group consisting of phosphates, aluminum salts and weak acid salts. Illustratively, the weak acid salt is selected from at least one of carbonate, oxalate and the like, such as at least one of sodium carbonate, potassium carbonate, sodium phosphate, aluminum sulfate.
Preferably, the filter residue obtained after filtration is collected for further processing.
According to the embodiment of the invention, in the step (2), the vanadium precipitation treatment can also be carried out after the oxidant is added. The purpose of adding the oxidant in the invention is to convert low-valence vanadium in the saturated solution into high-valence vanadium, thereby facilitating the subsequent vanadium precipitation treatment.
Preferably, the oxidant is at least one selected from hydrogen peroxide, chlorate, perchlorate and the like.
According to an embodiment of the present invention, the molar ratio of the added amount of the oxidizing agent to the low-valent vanadium in the crude vanadium is 1 to 2, preferably 1 to 1.5.
According to an embodiment of the present invention, in the step (2), the vanadium precipitation treatment includes vanadium precipitation and pH adjustment.
According to the embodiment of the invention, the addition amount of the vanadium precipitation agent is 10-300% of the mass of the crude vanadium, and preferably 60-120%.
Preferably, the vanadium precipitation treatment can adopt the following steps: complexing and precipitating vanadium by using a first vanadium precipitating agent in a one-step method, and adjusting the pH value; or
And adjusting the pH value of the saturated solution by adopting a pH adjusting agent, and precipitating vanadium by adopting a second vanadium precipitation agent.
Preferably, the first vanadium precipitation agent is selected from organic acids. Illustratively, the organic acid is selected from at least one of tartaric acid, oxalic acid, malic acid, citric acid.
Preferably, the second vanadium precipitation agent is selected from ammonium salts of the organic acids mentioned above. Preferably, the second vanadium precipitation agent is selected from at least one of ammonium tartrate, ammonium oxalate, ammonium citrate and ammonium malate.
Preferably, the pH adjuster can be selected from pH adjusters known in the art, and the concentration and the amount of the pH adjuster are not particularly limited as long as the desired pH value can be obtained, such as ammonia, sulfuric acid, and the like.
Preferably, the pH of the saturated solution is adjusted to 7 to 9, preferably 8 to 9.
Preferably, the temperature of the precipitated vanadium is 10 to 95 ℃, preferably 30 to 50 ℃, for example 30 ℃.
According to an embodiment of the invention, the vanadium precipitation also requires stirring.
Preferably, the stirring time is 0.5 to 6 hours, preferably 1 to 3 hours, for example 1 hour, 2 hours, 3 hours.
According to an embodiment of the invention, in step (3), the filter cake is washed with the aim of washing off entrained and easily soluble substances therein.
Preferably, the washing is carried out with a washing solution comprising: pure water, ammonia water with the concentration of 9.5-10.5 percent (g/mL) and ammonium salt solution. Illustratively, the ammonium salt is selected from at least one of ammonium chloride, ammonium sulfate, and ammonium organic salt solutions.
Preferably, the washing solution is used in an amount of 0.1 to 8 times, preferably 1 to 4 times, the mass of the filter cake.
According to an embodiment of the present invention, in the step (4), the regenerant is selected from hydroxides containing metal ions. Illustratively, the regenerant is selected from at least one of calcium hydroxide, calcium oxide, barium hydroxide, barium oxide, and the like.
According to an embodiment of the present invention, the amount of the regenerant added is 0.5 to 1.5 times, preferably 1 to 1.2 times, for example, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2 times of the molar amount of the acid radical ions in the filtrate after vanadium precipitation.
According to an embodiment of the invention, the acid ions comprise the sum of the acid ions in the added first vanadium precipitation agent or the sum of the acid ions in the added second vanadium precipitation agent and the pH regulator.
According to an embodiment of the invention, the temperature of the regeneration is between 10 and 90 ℃, preferably between 30 and 50 ℃.
According to an embodiment of the invention, the regeneration time is between 1 and 6h, preferably between 3 and 4h.
According to an embodiment of the invention, the stirring speed for the regeneration is between 100 and 1000r/min, preferably between 300 and 500r/min.
In the invention, the regeneration principle is that metal ions (such as calcium ions and barium ions) in the regenerant can be combined with acid radical ions in the filtrate after vanadium precipitation to form metal precipitated salt, and hydroxide ions in the regenerant enter the solution again. The metal precipitated salt can be changed into metal oxide again through high-temperature calcination, and recycling is realized.
According to an embodiment of the present invention, the concentration of acid ions in the regeneration liquid is less than 0.1wt%. Preferably, the pH value of the regeneration liquid is 13-14.
According to an embodiment of the present invention, the yield of the crude vanadium is 95 to 99.9%, preferably 98 to 99.9% by using the above purification method.
According to an embodiment of the present invention, the purification method further comprises: (5) And (4) recrystallizing the product obtained in the step (3) to obtain a purified vanadium-containing product.
According to an embodiment of the invention, the recrystallization comprises: dissolving, cooling and crystallizing.
According to an embodiment of the present invention, in the recrystallization, a recrystallization liquid is used for dissolution. Preferably, the recrystallization liquid is at least one selected from water, ammonia water and ammonium salt solution.
Illustratively, the ammonium salt solution is selected from at least one of ammonium chloride, ammonium sulfate and ammonium oxalate.
Preferably, the mass concentration of ammonium in the ammonium salt solution is 0.1-5%.
According to an embodiment of the present invention, in the step (5), the recrystallization liquid may be reused.
Preferably, the dissolution conditions of the recrystallization include: the temperature is 80-100 ℃, preferably 90-95 ℃; the time is 0.5 to 3 hours, preferably 1 to 2 hours; the stirring speed is 100 to 1000r/min, preferably 300 to 500r/min.
Preferably, the cooling crystallization conditions of recrystallization include: the temperature is 5-40 ℃, preferably 10-30 ℃; the time is 0.5 to 5 hours, preferably 2 to 4 hours.
The invention also provides application of the purification method in preparation of ammonium metavanadate or vanadium pentoxide.
The invention also provides the ammonium metavanadate prepared by the purification method.
According to an embodiment of the present invention, the yield of the ammonium metavanadate is 95 to 99.9%, preferably 98 to 99.9%.
According to an embodiment of the present invention, the purity of the ammonium metavanadate is not less than 99%, preferably 99% to 99.9%.
The invention also provides vanadium pentoxide prepared by adopting the ammonium metavanadate.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention realizes the recycling of the vanadium precipitation liquid and the recrystallization liquid by a simple method through an innovative method and design, realizes closed cycle of the whole process, does not need to treat and discharge waste water, and hardly has vanadium loss. The method has the advantages of low cost, low energy consumption, short flow and easy operation. The method has the advantages of simple process, short flow, few steps, no need of adding the vanadium precipitation agent for multiple times in the vanadium precipitation process, only need of adjusting the pH value once and less time consumption.
2. By adopting the purification method, no wastewater is discharged in the whole process, and the liquid phase realizes internal recycling. Solves the treatment problem of high ammonia nitrogen and high salt wastewater, not only is environment-friendly, but also greatly reduces the process cost and breaks through the bottleneck of large-scale industrial application.
3. The filter residue generated by the purification method of the invention can be reused.
4. In the traditional method, the loss of vanadium is inevitable and not low, but the purification method of the invention is adopted to purify and treat the ammonium metavanadate containing impurities, the vanadium loss is almost avoided in the purification process, the filtrate after vanadium precipitation is always circulated in the process and cannot be discharged outside, and the purity of the ammonium metavanadate product prepared by the invention can reach more than 99.9 percent.
5. The ammonium metavanadate product prepared by the purification method has low temperature and low energy consumption in the process of dissolving and precipitating vanadium; the purification treatment cost of each ton of product is lower than 5000 yuan, and the cost is low.
6. The precipitator of the invention can complex impurities and treat various impurities simultaneously, and the vanadium precipitation rate is high.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Taking 51g of strong ammonia water, adding 450g of water for even dilution, adding 25g of sodium hydroxide as an alkaline solution, adding 80g of ammonium metavanadate with the purity of 95%, and stirring and dissolving for 1 hour at the temperature of 30 ℃; filtering, heating the filtrate to 50 ℃, and performing vanadium precipitation treatment: adding 60g of oxalic acid while stirring, adjusting the pH value to 8 by using ammonia water, and precipitating vanadium for 3h. Filtering while the solution is hot, washing a filter cake by 100g of pure water, and drying the filter cake at the temperature of between 40 and 60 ℃ to obtain an ammonium metavanadate product, wherein the vanadium precipitation rate is 99 percent and the purity is 99.5 percent.
Example 1a
And (3) regeneration: adding 2ml of ammonia water into the filtrate obtained after vanadium precipitation in the embodiment 1 to promote the conversion of oxalate; adding calcium oxide with the molar ratio of the calcium oxide to the oxalate of 1, stirring and regenerating for 4 hours at 50 ℃, performing suction filtration to obtain 450ml of filtrate, washing the filter cake with 50ml of water, and combining the washing liquid and the filtrate. The washing liquid and filtrate were used for purification in example 1 as a recovered alkaline solution, and the pH was 13 to 14.
And then, according to the amount of the ammonium metavanadate crystallized in the embodiment 1, adding ammonium metavanadate with the purity of 95%, purifying according to the purification method of the embodiment 1 to obtain a product, and obtaining a recovered alkaline solution product after the 2 nd regeneration by adopting the method, wherein the vanadium precipitation rate of the recovered alkaline solution product is 97.53%, and the purity of the recovered alkaline solution product is 99.9%.
In order to further verify the recycling effect of the washing liquid and the filtrate as the recycled alkaline solution, taking the washing liquid and the filtrate after the 2 nd regeneration as the alkaline solution in the step 1, continuously adding ammonium metavanadate with the purity of 95%, repeating the dissolving, regenerating and vanadium precipitating processes, repeating the vanadium precipitation of the washing liquid and the filtrate after the 3 rd and 4 th regeneration, and measuring the vanadium precipitation rate of the recycled alkaline solution for vanadium precipitation as follows: 97.29%,99.6%,99.9%; the purity of the ammonium metavanadate product is 99.9%.
Example 2
Precipitating vanadium: taking 51g of strong ammonia water, adding 450g of water for even dilution, adding 5.5g of sodium hydroxide as an alkaline solution, adding 26g of ammonium metavanadate with the purity of 95%, and stirring and dissolving for 1h at the temperature of 30 ℃; filtering, heating the filtrate to 50 ℃, and performing vanadium precipitation treatment: adding 60g of citric acid while stirring, adjusting the pH value to 8 by using ammonia water, and precipitating vanadium for 3h. Filtering while the solution is hot, washing a filter cake by 50g of pure water, and drying the filter cake at the temperature of between 40 and 60 ℃ to obtain an ammonium metavanadate product, wherein the vanadium precipitation rate is 98.02 percent and the purity is 99.9 percent.
Example 3
Taking 51g of strong ammonia water, adding 450g of water for even dilution, adding 25g of sodium hydroxide as an alkaline solution, adding 90g of ammonium metavanadate with the purity of 95%, adding 5g of sodium carbonate, dissolving at 30 ℃ for removing impurities for 1 hour, and filtering; and (3) carrying out vanadium precipitation treatment on the filtrate at 50 ℃: adding oxalic acid and citric acid under stirring for complexing and precipitating vanadium, wherein the amount of the oxalic acid is 60g, the amount of the citric acid is 20g, adjusting the pH value to be 8-9 by using ammonia water, and stirring for 3 hours; washing the filter cake with 50g of pure water, drying at 40-60 ℃ to obtain an ammonium metavanadate product, wherein the vanadium precipitation rate is 96.01 percent and the purity is 99.5 percent;
example 3a
And (3) regeneration: 5ml of ammonia water was added to the filtrate after precipitation of vanadium in example 3 to promote the conversion of oxalate and citrate. Adding 66.2g of calcium oxide, stirring and regenerating for 4 hours at 50 ℃, filtering to obtain 440ml of filtrate, washing the filter cake with 60ml of water, and combining the washing liquid and the filtrate to obtain regenerated alkaline solution with the pH value of 13-14. And adding 80g of ammonium metavanadate with the purity of 95%, dissolving, filtering to remove impurities, adding oxalic acid, adjusting the pH value, crystallizing, and repeating the vanadium precipitation process. The vanadium precipitation rate is 99.9 percent and the purity is 99.5 percent.
Example 4
Taking 51g of strong ammonia water, adding 450g of water for dilution, adding 16g of sodium hydroxide, adding 58g of ammonium metavanadate with the purity of 98% (wherein the proportion of tetravalent vanadium ions is 5%), dissolving at 30 ℃ for removing impurities for 1h, and filtering; and (3) carrying out vanadium precipitation treatment on the filtrate at 50 ℃: adding 6g of oxidant sodium chlorate while stirring, oxidizing low-valence vanadium ions, then adding oxalic acid for complexing and precipitating vanadium, wherein the amount of oxalic acid is 60g, adjusting the pH value to 8, stirring for 3h, washing a filter cake by 50g of pure water, and drying at 40-60 ℃ to obtain an ammonium metavanadate product, wherein the vanadium precipitation rate is 98.26 percent and the purity is 99.5 percent.
Example 5
Taking 51g of strong ammonia water, adding 450g of water for dilution, adding 16g of sodium hydroxide, adding 57g of ammonium metavanadate with the purity of 95%, dissolving at 30 ℃ for removing impurities for 1h, and filtering; and (3) carrying out vanadium precipitation treatment on the filtrate at 50 ℃ under stirring: adding oxalic acid with the amount of 60g for complexing and precipitating vanadium, adjusting the pH value to 8-9 by ammonia water, stirring for 3h, washing a filter cake by 50g of pure water, drying at 40-60 ℃ to obtain an ammonium metavanadate product, and measuring the vanadium precipitation rate to be 93.18% and the purity to be 99.5%.
Example 5a
And (3) regeneration: adding 37.8g of calcium oxide and 70g of barium hydroxide into the filtrate obtained after vanadium precipitation in example 5, stirring and regenerating at 50 ℃ for 4 hours, carrying out suction filtration to obtain 450ml of filtrate, washing the filter cake with 50ml of water, and combining the washing liquor and the filtrate. The regenerated alkaline solution is obtained, and the pH value is 13-14. And adding 57g of ammonium metavanadate with the purity of 95%, dissolving, filtering to remove impurities, adding 60g of oxalic acid, adjusting the pH value, crystallizing, and repeating the vanadium precipitation process. The vanadium deposition rate is 96.74 percent and the purity is 99.5 percent.
Example 6
Taking 450g of water, adding 16g of sodium hydroxide, adding 57g of 98% ammonium heteropolyvanadate, dissolving at 30 ℃ to remove impurities for 1 hour, and filtering; and (3) carrying out vanadium precipitation treatment on the filtrate at 30 ℃: adding 30g of ammonium oxalate for complexing and precipitating vanadium under stirring, adjusting the pH value to 8 by using ammonia water, and stirring for 3 hours; washing the filter cake with 200g of pure water, drying at 40-60 ℃ to obtain an ammonium metavanadate product, wherein the vanadium precipitation rate is 99.31 percent and the purity is 99.9 percent.
Example 7
Taking 450g of water, adding 16g of sodium hydroxide, adding 57g of ammonium metavanadate with the purity of 95%, dissolving at 30 ℃ to remove impurities for 1h, and filtering; and (3) carrying out vanadium precipitation treatment on the filtrate at 30 ℃: adding 50g of tartaric acid for complexing and precipitating vanadium under stirring, adjusting the pH value to 8 by using ammonia water, and stirring for 3 hours; washing the filter cake with 200g of pure water, drying at 40-60 ℃ to obtain an ammonium metavanadate product, wherein the vanadium precipitation rate is 99.9 percent, and the purity is more than 99.5 percent.
And (3) recrystallization: 25g of the product is taken, 500g of water is used for dissolving for 1 hour at the temperature of 90 ℃, the solution is filtered while the solution is hot, and the filtrate is cooled to 30 ℃ for recrystallization for 2 hours. White ammonium metavanadate is separated out, filtered and dried to obtain a high-purity product, and the crystallization rate is 96.09 percent and the purity is more than 99.9 percent.
ICP detection is carried out on the high-purity products of the above examples, and the detection results are shown in Table 1.
ICP test instrument: IRIS Advantage 1000ICP-AES plasma atomic emission spectrometer.
TABLE 1
| Element(s) | Raw material containing miscellaneous vanadium | Example 1 | Example 2 | Example 7 |
| Al(ppm) | 500 | 10 | 10 | 10 |
| As(ppm) | 1 | 1 | 1 | 1 |
| Be(ppm) | 1 | 1 | 1 | 1 |
| Ca(ppm) | 330 | 23 | 17 | 10 |
| Cd(ppm) | 4 | 1 | 1 | 1 |
| Co(ppm) | 10 | 10 | 10 | 10 |
| Cr(ppm) | 950 | 53 | 10 | 12 |
| Cu(ppm) | 870 | 22 | 5 | 10 |
| Fe(ppm) | 1500 | 20 | 15 | 15 |
| K(ppm) | 1200 | 46 | 38 | 44 |
| Li(ppm) | 5 | 5 | 5 | 5 |
| Mg(ppm) | 530 | 10 | 10 | 10 |
| Mn(ppm) | 10 | 10 | 10 | 10 |
| Mo(ppm) | 500 | 10 | 10 | 10 |
| Na(ppm) | 100 | 20 | 10 | 32 |
| Ni(ppm) | 840 | 10 | 10 | 10 |
| P(ppm) | 10 | 10 | 10 | 10 |
| Pb(ppm) | 10 | 10 | 10 | 10 |
| Sb(ppm) | 10 | 10 | 10 | 10 |
| Si(ppm) | 500 | 20 | 20 | 20 |
| Sn(ppm) | 1 | 1 | 1 | 1 |
| Ti(ppm) | 5 | 5 | 5 | 5 |
| Zn(ppm) | 5 | 5 | 5 | 5 |
| Ammonium metavanadate (%) | 95 | 99.50 | 99.90 | 99.90 |
The results in table 1 show that the content of impurity ions in the crude vanadium is greatly reduced after the purification by the process of the present invention, and the purity of ammonium metavanadate can reach more than 99.5%. As can be seen from Table 1, the product purified by the purification method of the present invention has high purity. From this, it is understood that the purification method of the present invention is excellent in adaptability.
As can be seen from examples 1a, 3a and 5a, the regenerated alkaline solution of the present invention has stable impurity removal effect after repeated circulation.
It can be seen from comparing example 1 with example 7 that the impurities, such as chromium, calcium, etc., can be further reduced by recrystallization, which can meet different requirements for the purified product.
The above description is that of the exemplary embodiments of the invention. However, the scope of protection of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A method for purifying crude vanadium, characterized in that the method comprises the following steps:
(1) Dissolving crude vanadium in an alkaline solution until a saturated solution is obtained;
(2) After the saturated solution is subjected to vanadium precipitation treatment, crystals are separated out from the saturated solution;
(3) Filtering the saturated solution with the precipitated crystals to obtain a filter cake and a filtrate after vanadium precipitation, and washing the filter cake to obtain a purified vanadium-containing product; optionally, the step of (a) is carried out,
(4) Adding a regenerant into the filtrate obtained after vanadium precipitation in the step (3), reacting and filtering to obtain a regenerated solution; and (2) using the regeneration liquid as an alkaline solution for dissolving crude vanadium in the step (1).
2. The purification method according to claim 1, wherein the crude vanadium is at least one selected from the group consisting of ammonium metavanadate, ammonium polyvanadate, sodium polyvanadate and vanadium pentoxide containing impurities.
Preferably, the impurities are selected from at least one of Al, ca, co, cr, cu, fe, K, mg, mn, mo, na, si.
Preferably, the impurity content in the crude vanadium is 0.1 to 10wt%, preferably 0.5 to 5wt%.
Preferably, the vanadium in the crude vanadium comprises low-valent vanadium, the low-valent vanadium accounting for 0.1 to 10wt%, preferably 0.5 to 5wt%, of the total amount of vanadium.
3. Purification method according to claim 1 or 2, characterised in that the dissolution is carried out under stirring. Preferably, the stirring speed is 100 to 1000r/min, preferably 300 to 500r/min.
Illustratively, the temperature of the dissolution is 10 to 95 ℃.
Preferably, the dissolution time is 1 to 120min, preferably 30 to 60min.
Preferably, the alkaline solution is selected from a mixed solution of ammonia and a base.
Preferably, the base is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
Preferably, the alkaline solution contains ammonia in an amount of 0 to 25% by mass, preferably 1 to 5% by mass, and more preferably 1.5 to 3% by mass, respectively.
Preferably, the alkali is present in the alkaline solution in a mass fraction of 0 to 15%, preferably 2 to 7.5%, and more preferably 2 to 5%.
Preferably, the ratio of the mass of the crude vanadium to the total mass of ammonia and alkali in the alkaline solution is 2 to 5.
4. The purification method according to any one of claims 1 to 3, wherein the saturated solution is further subjected to impurity removal. Preferably, the impurity removal comprises preliminary filtration after adding a precipitating agent into the saturated solution to remove part of the impurities. Preferably, after the preliminary filtration, a residue and a saturated solution after filtration are obtained.
Preferably, the precipitating agent is selected from the group consisting of phosphates, aluminum salts and weak acid salts. Illustratively, the weak acid salt is selected from at least one of carbonate, oxalate and the like, such as at least one of sodium carbonate, potassium carbonate, sodium phosphate and aluminum sulfate.
Preferably, the filter residue obtained after filtration is collected for further processing.
5. The purification method according to any one of claims 1 to 4, wherein in the step (2), the oxidizing agent is added and then vanadium precipitation is performed.
Preferably, the oxidant is at least one selected from hydrogen peroxide, chlorate, perchlorate and the like.
Preferably, the molar ratio of the addition amount of the oxidant to the low-valent vanadium in the crude vanadium is 1-2, preferably 1-1.5.
Preferably, in the step (2), the vanadium precipitation treatment comprises vanadium precipitation and pH adjustment.
Preferably, the addition amount of the vanadium precipitation agent is 10-300% of the mass of the crude vanadium, and preferably 60-120%.
Preferably, the vanadium precipitation treatment can adopt the following steps: complexing and precipitating vanadium by using a first vanadium precipitating agent in a one-step method, and adjusting the pH value; or
And adjusting the pH value of the saturated solution by adopting a pH regulator, and precipitating vanadium by adopting a second vanadium precipitation agent.
Preferably, the first vanadium precipitation agent is selected from organic acids. Illustratively, the organic acid is selected from at least one of tartaric acid, oxalic acid, malic acid, and citric acid.
Preferably, the second vanadium precipitation agent is selected from ammonium salts of the above organic acids. Preferably, the second vanadium precipitating agent is selected from at least one of ammonium tartrate, ammonium oxalate, ammonium citrate and ammonium malate.
Preferably, the pH of the saturated solution is adjusted to 7 to 9, preferably 8 to 9.
Preferably, the temperature of the precipitated vanadium is 10 to 95 ℃, preferably 30 to 50 ℃, for example 30 ℃.
Preferably, the vanadium precipitation also requires stirring.
Preferably, the stirring time is 0.5 to 6 hours, preferably 1 to 3 hours.
Preferably, in step (3), the filter cake is washed.
Preferably, the washing is carried out with a washing solution: pure water, ammonia water with the concentration of 9.5-10.5 percent (g/ml) and ammonium salt solution.
Preferably, the amount of the washing solution is 0.1 to 8 times the mass of the filter cake.
6. The purification method according to any one of claims 1 to 5, wherein in the step (4), the regenerant is selected from hydroxides containing metal ions.
Illustratively, the regenerant is selected from at least one of calcium hydroxide, calcium oxide, barium hydroxide, barium oxide, and the like.
Preferably, the addition amount of the regenerant is 0.5-1.5 times of the molar amount of the acid radical ions in the filtrate after vanadium precipitation.
Preferably, the acid radical ions comprise the sum of the acid radical ions in the added first vanadium precipitation agent or the sum of the acid radical ions of the added second vanadium precipitation agent and the pH adjusting agent.
Preferably, the temperature of the regeneration is 10 to 90 ℃.
Preferably, the regeneration time is 1 to 6 hours.
Preferably, the stirring speed of the regeneration is 100 to 1000r/min.
Preferably, the concentration of acid ions in the regeneration liquid is less than 0.1wt%.
Preferably, the pH value of the regeneration liquid is 13-14.
7. The purification method according to any one of claims 1 to 6, further comprising: (5) And (4) recrystallizing the product obtained in the step (3) to obtain a purified vanadium-containing product.
Preferably, the recrystallization comprises: dissolving, cooling and crystallizing.
Preferably, in the recrystallization, a recrystallization solution is used for dissolution. Preferably, the recrystallization liquid is at least one selected from water, ammonia water and ammonium salt solution.
Illustratively, the ammonium salt solution is selected from at least one of ammonium chloride, ammonium sulfate and ammonium oxalate.
Preferably, the mass concentration of ammonium in the ammonium salt solution is 0.1-5%.
Preferably, in the step (5), the recrystallization solution may be reused.
Preferably, the dissolution conditions of the recrystallization include: the temperature is 80-100 ℃; the time is 0.5 to 3 hours; the stirring speed is 100-1000 r/min.
Preferably, the cooling crystallization conditions for recrystallization include: the temperature is 5-40 ℃; the time is 0.5 to 5 hours.
8. Use of the purification process according to any one of claims 1 to 7 for the preparation of ammonium metavanadate or vanadium pentoxide.
9. Use according to claim 8, wherein the ammonium metavanadate is prepared by the purification method according to any one of claims 1 to 7.
Preferably, the yield of the ammonium metavanadate is 95 to 99.9 percent.
Preferably, the purity of the ammonium metavanadate is not less than 99%.
10. Vanadium pentoxide characterized in that it is prepared using ammonium metavanadate according to claim 9.
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| CN116375084B (en) * | 2023-05-30 | 2023-08-01 | 寰泰储能科技股份有限公司 | Preparation method of vanadium pentoxide |
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