CN114275815B - Method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium liquid - Google Patents
Method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium liquid Download PDFInfo
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- CN114275815B CN114275815B CN202111546650.2A CN202111546650A CN114275815B CN 114275815 B CN114275815 B CN 114275815B CN 202111546650 A CN202111546650 A CN 202111546650A CN 114275815 B CN114275815 B CN 114275815B
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- Prior art keywords
- vanadium
- sodium
- solution
- reducing agent
- purity
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 87
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000001376 precipitating effect Effects 0.000 title claims abstract description 12
- 230000001603 reducing effect Effects 0.000 title claims abstract description 10
- 239000007788 liquid Substances 0.000 title claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 115
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000001556 precipitation Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 6
- 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 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical group [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 5
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 5
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 2
- 229940001482 sodium sulfite Drugs 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims 1
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical compound [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 claims 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000006012 monoammonium phosphate Substances 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 58
- 239000012535 impurity Substances 0.000 description 50
- 239000011651 chromium Substances 0.000 description 22
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 7
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 125000005287 vanadyl group Chemical group 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- LXMQZGGLHVSEBA-UHFFFAOYSA-N chromium;trihydrate Chemical compound O.O.O.[Cr] LXMQZGGLHVSEBA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- -1 vanadate ions Chemical class 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- CNPZUUBJPMQACQ-UHFFFAOYSA-N [O-2].[O-2].[O-2].O.O.[Na+].[V+5] Chemical compound [O-2].[O-2].[O-2].O.O.[Na+].[V+5] CNPZUUBJPMQACQ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 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 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention relates to the technical fields of vanadium chemical industry and high-purity vanadium pentoxide preparation, in particular to a method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium liquid. The method comprises the following steps: providing a sodium vanadium solution, adding acid and a reducing agent, adjusting the pH value to 2-3, adding a first ammonium salt, reacting, filtering to obtain a vanadium precipitation filter cake after the reaction is finished, pulping and washing the filter cake with deionized water, and then drying; and (3) dissolving the dried product in a sodium hydroxide solution, controlling the final pH value to be between 10.5 and 12, stirring for reaction, filtering to obtain a gray green filter cake and a colorless vanadium solution, adding a second ammonium salt into the colorless vanadium solution, filtering, washing and drying after the reaction is finished to obtain a white solid, and roasting the white solid to obtain vanadium pentoxide. According to the method for preparing the high-purity vanadium pentoxide by the sodium vanadium solution reduction precipitation, the high-purity vanadium pentoxide with the purity of more than 99.99 weight percent can be prepared.
Description
Technical Field
The invention relates to the technical fields of vanadium chemical industry and high-purity vanadium pentoxide preparation, in particular to a method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium liquid.
Background
At present, the method for preparing high-purity vanadium pentoxide by taking sodium vanadium solution as a raw material mainly comprises a re-dissolution method, a chemical impurity removal method, an extraction method, an ion exchange method, a chlorination method and the like.
The method is characterized in that the method is based on the principle that vanadium ions have different precipitation characteristics in different pH environments, and the purpose of separating impurities can be achieved by utilizing the precipitation characteristics of the vanadium raw materials through multiple precipitation, dissolution and reprecipitation, wherein the vanadium precipitation method and precipitation products at the present stage mainly comprise the following steps: ① Hydrolyzing and precipitating vanadium-red cake, ② acid ammonium salt and precipitating vanadium-APV, ③ weak acid ammonium salt and precipitating vanadium-SAV, ④ weak alkaline and precipitating vanadium-AMV. Thus, the re-dissolution process can be roughly summarized as "initial vanadium liquor- & gt APV/SAV/AMV/red cake- & gt alkali chemical impurity removal- & gt AMV- & gt vanadium pentoxide". For example, patent applications CN102603000a and CN102730757a both disclose a method for preparing high-purity vanadium pentoxide from ammonium metavanadate, which mainly comprises the following steps: the crude product AMV, the re-dissolution chemical impurity removal, AMV and vanadium pentoxide, wherein magnesium salt is also adopted as an impurity removal agent in the process, the cost of the process raw materials is high, and the process flow is complex. Patent application CN109502644A discloses a process of 'strong acid vanadium precipitation-ammonia water dissolution vanadium precipitation-calcination', which can prepare vanadium pentoxide with purity of 99.9 percent, and has simple process flow and no chemical impurity removal, but has the main problems of overlarge sulfuric acid consumption in the strong acid vanadium precipitation process and extremely high requirements on equipment in industrial production. The technological route adopted in the article Hou Haijun, the preparation technical research of high-purity ammonium metavanadate [ J ]. Iron and steel vanadium-titanium, 2013 ] is as follows: the method comprises the steps of vanadium solution, APV, re-dissolution chemical impurity removal and AMV, wherein aluminum sulfate is adopted for chemical impurity removal in the process, the content of Si and Cr in the finally prepared ammonium metavanadate still remains 100ppm, the requirement of the market on high-purity vanadium is not met, the purity of the AMV prepared by the process is low, the process flow is complex, and silicon slag removal is difficult to treat. In addition, patent application CN106044853a discloses a process of "crude AMV-acidification-APV-ammonia dissolution vanadium precipitation-calcination", which is not used for chemical impurity removal, but has the disadvantages of excessively long process flow and extremely high cost. In combination, the redissolution method combines the advantages of various precipitated vanadium, so that the vanadium and impurities are transferred for multiple times in a solid phase and a liquid phase, the impurity removal range is wide, the operation is simple, and the process stability is good. However, the existing re-dissolving process is often matched with a chemical impurity removing method, so that the problems of poor deep impurity removing effect, low product purity, complex process flow, easiness in introducing impurity ions, increased vanadium loss caused by repeated vanadium precipitation, increased discharge of vanadium precipitation wastewater and the like exist.
The chemical impurity removing method is based on the principle that under certain reaction conditions, a chemical impurity removing agent is added into vanadium solution to cause the added impurity removing agent to have precipitation reaction with impurities, and after filtration, vanadium and impurities are precipitated and separated. The impurities in the vanadium solution with different properties are different, and the main impurities in the sodium vanadium solution are Si, P, fe, ca, cr and other elements, wherein Fe 3+ and Ca 2+ exist in a cationic form, siO 3 2-、PO4 3-、CrO4 2- exists in an anionic form and the like. The chemical impurity removing agent for removing the anionic impurities mainly comprises calcium salt, magnesium salt, aluminum salt, ferric salt and the like, and the chemical impurity removing agent for removing the cationic impurities mainly comprises sulfide, oxalate, other flocculating agents, chelating agents and the like. The chemical impurity removal method is simple to operate, has low requirements on equipment, and is suitable for industrial mass production. However, the chemical impurity removal capability is limited, deep impurity removal is not achieved, new impurities are easy to bring in, the types and the contents of impurities contained in different vanadium sources are different, the adding amount of the impurity removal agent is not easy to control when chemical impurity removal is adopted, the impurity removal is not thorough, and the quality of a final product is unstable. In addition, the addition of the individual impurity removing agents reacts with vanadium, resulting in the loss of vanadium. As described in patent application CN103787414B, CN106044853A, CN109336177B, CN108975402B, chemical impurity removal methods are all used.
The extraction method mainly utilizes the solubility difference of vanadium in different organic solvents to selectively extract vanadium in a vanadium solution into an organic phase, and then uses a stripping agent to strip vanadium into a water phase, so that vanadium and impurities are separated, the vanadium solution is purified, and a method for preparing high-purity vanadium pentoxide by extracting heteropolyacid impurities with amines is disclosed in patent application CN201310377023. X. The extraction method has the advantages of good selectivity, small vanadium loss, high purity of the obtained product, stable quality, no need of adding any impurity removing agent, no introduction of new impurities, recycling of the extracting agent and the like. However, the extraction and purification process needs to be subjected to multi-stage extraction, back extraction and other procedures, so that the production process is complicated, the production period is prolonged, meanwhile, the extractant is expensive and easy to lose efficacy, the organic phase solvent is inflammable and toxic, the environmental pollution is serious, the extraction condition is severe and the like, and the method is mainly used for recovering vanadium such as stone coal (such as patent application CN 106282538A), low-vanadium steel slag, waste catalyst and the like.
The ion exchange method is to make vanadate ions and active functional groups on the ion exchange resin undergo ion exchange reaction by contacting the ion exchange resin with vanadium-containing solution. After the adsorption saturation, the vanadium on the resin is desorbed by a resolving agent, and most of the ion exchange resins are strong alkaline quaternary amine type anion exchange resins. The ion exchange method has good adsorption effect and selectivity, and can effectively remove cationic impurities. The ion exchange method has the defects of complicated operation, large amount of wastewater generated during resin desorption and regeneration, long production period, small production capacity and the like. Meanwhile, a small amount of impurity ions are replaced with active functional groups in the ion exchange process, so that the aim of complete purification cannot be achieved.
The high-purity vanadium pentoxide is prepared by a chlorination method, wherein vanadium slag, an intermediate product of vanadium, a vanadium catalyst and the like are subjected to chlorination reaction with a chlorinating agent, so that an intermediate product of crude vanadium oxychloride (VOCl 3) is generated. Based on the difference of boiling points of vanadium oxychloride and chlorides of impurities such as iron, silicon, magnesium, manganese, calcium, aluminum, sodium and the like, high-purity vanadium oxychloride can be obtained through rectification, and is subjected to hydrolysis or ammonium salt precipitation and then calcined to obtain high-purity vanadium pentoxide. Or the vanadium oxychloride is subjected to dust removal, leaching, sedimentation and rectification to obtain high-purity vanadium pentoxide powder under the action of oxygen-enriched air and a catalyst. The preparation of the high-purity vanadium pentoxide by the chlorination method has great advantages from the principle of purification and impurity removal, such as thorough impurity separation, no ammonia-nitrogen-containing wastewater, high product purity, small vanadium loss rate and the like. However, the chlorination method has higher requirements on equipment, personal safety and operation environment, and most of related researches are still in the laboratory research and development stage, and have a longer history from industrial application. Such as patent application CN109835949A, CN109835950A, CN110683580A, CN108622936A, CN106676289a, etc.
In conclusion, a set of preparation process which is simple in flow, efficient in impurity removal and low in cost does not exist at present for preparing high-purity vanadium pentoxide by using the sodium vanadium solution.
Disclosure of Invention
The invention aims to overcome the defects of poor impurity removal effect, low product purity, complex process flow or introduction of impurity ions in the existing process for preparing vanadium pentoxide by taking sodium vanadium solution as a raw material, and provides a method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium solution.
In order to achieve the above purpose, the invention provides a method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium liquid, which comprises the following steps:
(1) Providing sodium vanadium solution, adding acid and a reducing agent, regulating the pH value to be 2-3, and then adding a first ammonium salt for reaction, wherein the stoichiometric ratio of the reducing agent to Cr in the sodium vanadium solution is 1.2-6, and the ratio is m (NH 3): the ammonium addition coefficient of m (V) is 0.45-0.65, the reaction temperature is 75-100 ℃ and the reaction time is 0.5-3h, after the reaction is finished, filtering to obtain a vanadium precipitation filter cake, pulping and washing the filter cake with deionized water, and then drying;
(2) Dissolving the dried product in the step (1) in a sodium hydroxide solution, controlling the final pH value to be between 10.5 and 12, stirring and reacting for 3 to 12 hours at the temperature of 90 to 100 ℃, filtering to obtain a filter cake and a colorless vanadium solution, and adding a second ammonium salt into the colorless vanadium solution, wherein the pH value is controlled to be between 90 and 100 ℃, and the second ammonium salt is prepared according to the following formula (M) (NH 3): the ammonium addition coefficient of m (V) is 0.65-1, the reaction is carried out for 0.5-3h, the white solid is obtained by filtering, washing and drying after the reaction is finished, and the white solid is roasted for 1-3h at the temperature of 450-600 ℃ to obtain the vanadium pentoxide.
The invention provides a process for reducing acidic ammonium salt vanadium precipitation (Si removal) -re-dissolution hydrolysis (Cr removal) -weak alkaline ammonium salt vanadium precipitation, which mainly adopts sodium vanadium solution as a raw material, and on the basis of the process for preparing high-purity vanadium pentoxide by a traditional re-dissolution method (also called repeated precipitation method), APV (namely acidic ammonium salt vanadium precipitation) is precipitated, and meanwhile, a reducing agent is added to reduce hexavalent chromium to obtain a dark green precipitate, and as the reducing agent preferentially reacts with hexavalent chromium ions in the vanadium solution, the hexavalent chromium ions are reduced to trivalent chromium ions, the coordination capacity of the trivalent chromium ions and silicon is extremely weak, the capability of combining silicon is lost after the hexavalent chromium is reduced to trivalent chromium, so that silicon remains in the solution in the vanadium precipitation process, and Si in the solid APV can be controlled below 20ppm at the moment, and the silicon removal rate is more than 99.9%. Dissolving the obtained dark green precipitate in alkali liquor, controlling the pH range of vanadium solution, completely hydrolyzing Cr 3+ under certain temperature and time conditions, and carrying out ammonia dissipation, cr 3+ hydrolysis and ammonia removal, wherein the content of Cr element in the solution can be reduced to below 5 ppm. Finally, weak alkaline ammonium salt vanadium precipitation is carried out on the vanadium solution after chromium removal to obtain high-purity AMV, and the AMV is roasted to obtain high-purity vanadium pentoxide with the purity of more than 99.99 weight percent.
Compared with the prior art, the invention has the following advantages:
(1) According to the method, on the basis of preparing metallurgical grade vanadium pentoxide by industrialized acid ammonium salt vanadium precipitation, the reduction of hexavalent chromium and the acid ammonium salt vanadium precipitation are synchronously carried out, and the novel process for preparing the high-purity vanadium pentoxide by a two-step method is provided, wherein the process does not relate to the common process steps of preparing the high-purity vanadium by chlorination, ion exchange, extraction, chemical impurity removal and the like, does not introduce impurity ions, does not increase new solid waste, does not pollute chlorine and organic matters, has simple process and low equipment requirements, is environment-friendly, and is closely attached to industrial production.
(2) The method of the invention advances the reduction step of chromium, eliminates the influence of Si and Cr content fluctuation in the raw materials on the process, and has strong raw material adaptability and small product quality fluctuation.
(3) The method realizes the deep and efficient separation of vanadium and chromium while preparing high-purity vanadium pentoxide, respectively obtains the products of chromium and vanadium, improves the comprehensive utilization of resources, and is an efficient and energy-saving technology.
(4) The purity of the vanadium pentoxide product prepared by the method is more than 99.99%, wherein the content of K, na and Si is less than 20ppm, cr is less than 5ppm, the content of other impurity elements is less than 20ppm, and the direct yield of vanadium is more than 70%. Can meet the requirements of different vanadium-based new materials on the purity of vanadium pentoxide. Compared with the existing high-purity vanadium technology in the market, the method has the advantages of high production efficiency, high product purity and high vanadium yield.
Drawings
FIG. 1 is a flow chart of a method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium solution.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As shown in FIG. 1, the two-step method for preparing high-purity vanadium pentoxide by using the sodium vanadium solution comprises the following steps:
(1) Providing sodium vanadium solution, adding acid and a reducing agent, regulating the pH value to be 2-3, and then adding a first ammonium salt for reaction, wherein the stoichiometric ratio of the reducing agent to Cr in the sodium vanadium solution is 1.2-6, and the ratio is m (NH 3): the ammonium addition coefficient of m (V) is 0.45-0.65, the reaction temperature is 75-100 ℃ and the reaction time is 0.5-3h, after the reaction is finished, filtering to obtain a vanadium precipitation filter cake, pulping and washing the filter cake with deionized water, and then drying;
(2) Dissolving the dried product in the step (1) in a sodium hydroxide solution, controlling the final pH value to be between 10.5 and 12, stirring and reacting for 3 to 12 hours at the temperature of 90 to 100 ℃, filtering to obtain a filter cake (grey green) and a colorless vanadium solution, and adding a second ammonium salt into the colorless vanadium solution, wherein the pH value is controlled to be between 90 and 100 ℃, and the following steps are as follows: the ammonium addition coefficient of m (V) is 0.65-1, the reaction is carried out for 0.5-3h, the white solid is obtained by filtering, washing and drying after the reaction is finished, and the white solid is roasted for 1-3h at the temperature of 450-600 ℃ to obtain the vanadium pentoxide.
In the invention, the sodium vanadium solution can be a vanadium-containing solution obtained by leaching a vanadium raw material containing silicon and chromium with deionized water or alkali. The vanadium feedstock containing silicon and chromium may be selected from at least one of the following: vanadium slag generated in the vanadium titano-magnetite smelting process, sodium roasting clinker, ammonium Polyvanadate (APV), ammonium Metavanadate (AMV), sodium polyvanadate (SAV), hydrolyzed red cakes or other crude vanadium oxides generated in the vanadium chemical process, and vanadium slag or intermediate products containing silicon and chromium generated in the vanadium extraction process of other vanadium-containing minerals.
In step (1), the acid added may be an inorganic acid, preferably sulfuric acid.
In step (1), the reducing agent may be at least one of a vanadium-containing reducing agent, a sulfur-containing reducing agent, and an organic reducing agent. In particular, the vanadium-containing reducing agent may be selected from vanadyl sulfate, vanadyl dioxide, vanadyl trichloride, vanadyl oxalate, vanadyl dioxide, vanadyl tetraoxide, vanadyl trioxide, and other inorganic or organic compounds containing trivalent vanadium, tetravalent vanadium. The sulfur-containing reducing agent may be selected from sulfur dioxide, sulfurous acid, sodium sulfite, sodium metabisulfite, sodium thiosulfate, hydrogen sulfide, sodium hydrosulfide, and the same forms of potassium, ammonium or other compounds containing low sulfur. The organic reducing agent may be selected from vitamin C, oxalic acid, formic acid, tartaric acid, citric acid, and other organic substances having reducing properties. Preferably, the reducing agent is at least one of vanadyl sulfate, sodium sulfite, and sodium metabisulfite.
In step (1), the pH is adjusted to 2-3, such as 2.0, 2.2, 2.5, 3.0, etc.
In step (1), the stoichiometric ratio of the reducing agent to Cr in the vanadium-containing solution is 1.2-6, such as 1.2, 3, 4.5, 6.0, etc. When the consumption of the reducing agent is lower than 1.2, the hexavalent chromium is incompletely reduced; if the amount is higher than 6.0, excessive reduction and loss of vanadium may be caused by the use of a non-tetravalent vanadium salt reducing agent.
In step (1), the following is performed according to m (NH 3): the ammonium addition coefficient of m (V) is 0.45-0.65, such as 0.45, 0.52, 0.58, 0.65, etc. The ammonium addition coefficient is too low, and the vanadium precipitation rate is low; the ammonium addition coefficient is too high, the ammonium salt loss is high, the vanadium precipitation wastewater treatment capacity is large, and the cost is high. As used herein, the term "ammonium addition factor" refers to the ratio of NH 3 added to the ammonium salt to the mass of V in the vanadium sodium salt solution.
In step (1), the reaction is a reduction reaction. The reduction reaction is carried out at 75-100deg.C, such as 75deg.C, 85deg.C, 95deg.C, 100deg.C, etc., and the reduction efficiency is low. The reduction reaction time is 0.5-3h, such as 0.5h, 1h, 2h, 3h, etc., and the reduction is incomplete if the time is too short.
In step (2), the final pH is controlled to be between 10.5 and 12, such as 10.5, 11, 11.5, 12, etc. Too low pH, insufficient hydrolysis of Cr 3+, and reduced Cr removal rate; when the pH value is too high, the phenomenon of chromium returning occurs, and part of chromium hydroxide is dissolved in alkali liquor.
In the step (2), the temperature of the reaction is in the range of 90-100deg.C, such as 90deg.C, 95deg.C, 98deg.C, 100deg.C, etc. When the temperature is high, the dissolution rate of APV is high, and meanwhile, the hydrolysis precipitation rate of Cr 3+ is also accelerated, so that the final chromium removal rate is improved.
In the step (2), the reaction time is 3-12h, such as 3h, 6h, 9h, 12h, etc. Too short time, incomplete deamination, affecting the final vanadium yield; the time is too long, and the energy consumption and the cost are increased.
In step (2), according to m (NH 3): the ammonium addition coefficient of m (V) is 0.65-1, such as 0.65, 0.77, 0.9, 1.0, etc. The ammonium addition coefficient is too low, and the vanadium precipitation rate is low; the ammonium addition coefficient is too high, the ammonium salt loss is high, the vanadium precipitation wastewater treatment capacity is large, and the cost is high. As used herein, the "ammonium addition factor" refers to the ratio of NH 3 added to the ammonium salt to the mass of V in the colorless vanadium solution.
In the step (2), the reaction after the addition of the second ammonium salt is carried out at the residual temperature of the colorless vanadium solution without additional heating.
In step (2), the reaction time after the addition of the second ammonium salt is 0.5 to 3 hours, such as 0.5 hours, 1 hour, 2 hours, 3 hours, etc. Too short time, incomplete vanadium precipitation and low vanadium precipitation yield.
In step (2), the baking temperature is 450-600deg.C, such as 450deg.C, 500 deg.C, 550 deg.C, 600 deg.C, etc. When the temperature is too low, the roasting is incomplete, and the materials are required to be continuously rolled in the roasting process; when the temperature is too high, the energy consumption is high.
In step (2), the roasting time is 1-3 hours, such as 1 hour, 1.5 hours, 2 hours, 3 hours, etc. Too short a roasting time, and incomplete decomposition of AMV; the roasting time is too long and the energy consumption is high.
In the present invention, the first ammonium salt and the second ammonium salt may be the same or different, preferably the same. Further, the first ammonium salt and the second ammonium salt may each independently be selected from at least one of ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium chloride, monoamine phosphate, diamine hydrogen phosphate, aqueous ammonia, and other ammonium group-containing inorganic compounds, preferably ammonium sulfate.
In the method of the present invention, as shown in fig. 1, the pH value of the filtrate obtained after filtration in step (1) is adjusted to 10.5-12, and then chromium hydroxide (Cr (OH) 3) can be obtained by heating and stirring, and then filtering and drying. In addition, the main component of the green-gray cake separated by filtration in step (2) is also chromium hydroxide (Cr (OH) 3). Therefore, the method can separate chromium products while realizing the preparation of the high-purity vanadium pentoxide.
The present invention will be described in detail by examples.
The sodium vanadium solution used in the following examples and comparative examples is vanadium leaching solution obtained by roasting vanadium slag generated in the smelting process of vanadium titano-magnetite through sodium treatment and leaching the vanadium slag by deionized water, wherein K is between 0.241g/L, na and 49.66g/L, si and 1.18g/L, cr and 2.15g/L, and TV is between 43.22g/L.
In the following examples and comparative examples, the mass percentages of the components in the vanadium pentoxide target product were detected using an inductively coupled plasma mass spectrometer (ICP-MS).
Example 1
The embodiment is used for explaining a method for preparing high-purity vanadium pentoxide by a two-step method of the sodium vanadium solution.
(1) 500Ml of sodium vanadium solution is measured, sulfuric acid is firstly added dropwise to adjust the pH value to be neutral, 3.54g of sodium metabisulfite is added, sulfuric acid is then added dropwise to control the pH value to be 2.0, 30.6g of ammonium chloride is then added, and the mixture is stirred at 75 ℃ for reaction for 3 hours. And after the reaction is finished, filtering to obtain a vanadium precipitation product, pulping and washing the vanadium precipitation product twice by deionized water, filtering and drying to obtain the APV.
(2) The dried APV is dissolved in sodium hydroxide solution, the pH value of the end point is controlled to be 10.5, the mixture is stirred and reacted for 12 hours at 90 ℃, and the mixture is filtered to obtain a dark green filter cake and 490ml of colorless vanadium solution, wherein the TV is 42.67g/L.
(3) 42.76G of ammonium chloride is added into the colorless vanadium solution, the mixture is stirred and reacted for 0.5h, and after the reaction is finished, the mixture is filtered, washed and dried to obtain a white solid.
(4) The dried white solid is roasted for 3 hours at 450 ℃ to obtain 31.7g of vanadium pentoxide, and the detected Si-0.0018%, cr < 0.0005%, K-0.0022%, na < 0.0005%, the purity of the vanadium pentoxide is more than 99.99%, and the direct vanadium yield is 82.2%.
Example 2
The embodiment is used for explaining a method for preparing high-purity vanadium pentoxide by a two-step method of the sodium vanadium solution.
(1) 500Ml of sodium vanadium solution is measured, sulfuric acid is firstly added dropwise to adjust the pH value to be neutral, 65ml of vanadyl sulfate solution with the concentration of 2.85mol/L is added, sulfuric acid is then added dropwise to control the pH value to be 2.2, 51.53g of ammonium bicarbonate (the content of NH 3 is about 21 wt%) is then added, and the mixture is stirred at the temperature of 85 ℃ for 2 hours for reaction. And after the reaction is finished, filtering to obtain a vanadium precipitation product, pulping and washing the vanadium precipitation product twice by deionized water, filtering and drying to obtain the APV.
(2) The dried APV is dissolved in sodium hydroxide solution, the pH value of the end point is controlled to be 11, the mixture is stirred and reacted for 9 hours at the temperature of 95 ℃, and a dark green filter cake and 540ml of colorless vanadium solution are obtained by filtration, wherein the TV is 38.17g/L.
(3) Adding 75.84g of ammonium bicarbonate into the colorless vanadium solution, stirring and reacting for 1h, and filtering, washing and drying after the reaction is finished to obtain a white solid.
(4) The dried white solid is roasted for 2 hours at 500 ℃ to obtain 30.9g of vanadium pentoxide, and the detected Si-0.0015%, cr < 0.0005%, K-0.0023%, na-0.0005%, the purity of the vanadium pentoxide is more than 99.99%, and the direct vanadium yield is 80.1%.
Example 3
The embodiment is used for explaining a method for preparing high-purity vanadium pentoxide by a two-step method of the sodium vanadium solution.
(1) 500Ml of sodium vanadium solution is measured, sulfuric acid is firstly added dropwise to adjust the pH value to be neutral, 17.6g of sodium sulfite is added, sulfuric acid is then added dropwise to control the pH value to be 2.5, 48.62g of ammonium sulfate is then added, and the mixture is stirred and reacted for 1h at 95 ℃. And after the reaction is finished, filtering to obtain a vanadium precipitation product, pulping and washing the vanadium precipitation product twice by deionized water, filtering and drying to obtain the APV.
(2) The dried APV is dissolved in sodium hydroxide solution, the pH value of the end point is controlled to be 11.5, the mixture is stirred and reacted for 6 hours at 98 ℃, and a dark green filter cake and 485ml of colorless vanadium solution are obtained by filtering, wherein the TV is 42.14g/L.
(3) 71.53G of ammonium sulfate is added into the colorless vanadium solution, stirred and reacted for 2 hours, and after the reaction is finished, the white solid is obtained through filtration, washing and drying.
(4) The dried white solid is roasted for 1.5 hours at 550 ℃ to obtain 30.3g of vanadium pentoxide, and the vanadium pentoxide has the purity of more than 99.99% and the direct vanadium yield of 78.6% by detection, wherein the content of Si-0.0008%, cr < 0.0005%, K-0.0011% and Na-0.0007% are all obtained.
Example 4
The embodiment is used for explaining a method for preparing high-purity vanadium pentoxide by a two-step method of the sodium vanadium solution.
(1) 500Ml of sodium vanadium solution is measured, sulfuric acid is firstly added dropwise to adjust the pH to be neutral, 23.45g of oxalic acid dihydrate is added, sulfuric acid is then added dropwise to control the pH to be 3.0, then 35.12g of ammonium carbonate (the NH 3 content is about 40 wt%) is added, and the mixture is stirred at 100 ℃ for reaction for 0.5h. And after the reaction is finished, filtering to obtain a vanadium precipitation product, pulping and washing the vanadium precipitation product twice by deionized water, filtering and drying to obtain the APV.
(2) The dried APV is dissolved in sodium hydroxide solution, the pH value of the end point is controlled to be 12, the mixture is stirred and reacted for 3 hours at 100 ℃, and a dark green filter cake and 490ml of colorless vanadium solution are obtained by filtration, wherein the TV is 41.04g/L.
(3) 50.27G of ammonium carbonate is added into the colorless vanadium solution, stirred and reacted for 3 hours, and filtered, washed and dried after the reaction is finished to obtain white solid.
(4) The dried white solid is roasted for 1h at 600 ℃ to obtain 29.6g of vanadium pentoxide, and the detected Si-0.0005%, cr < 0.0005%, K-0.0007%, na < 0.0005%, the purity of the vanadium pentoxide is more than 99.99%, and the direct vanadium yield is 76.8%.
Comparative example 1
The procedure of example 1 was followed except that in step (1), sodium metabisulfite, a reducing agent, was not added.
The finally prepared vanadium pentoxide product is detected to have Si-0.105%, cr < 0.002%, K-0.007%, na-0.005%, the purity of the vanadium pentoxide is about 99.8%, and the direct vanadium yield is 81.7%.
As can be seen from the above examples and comparative examples, the method for preparing high-purity vanadium pentoxide by the two-step method of the sodium vanadium pentoxide liquid can prepare high-purity vanadium pentoxide with purity of more than 99.99wt%, and can meet the requirements of various industries on the purity of vanadium sources.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (8)
1. The method for preparing high-purity vanadium pentoxide by reducing and precipitating sodium vanadium liquid is characterized by comprising the following steps of:
(1) Providing sodium vanadium solution, adding acid and a reducing agent, regulating the pH value to be 2-3, and then adding a first ammonium salt for reaction, wherein the stoichiometric ratio of the reducing agent to Cr in the sodium vanadium solution is 1.2-6, and the ratio is m (NH 3): the ammonium addition coefficient of m (V) is 0.45-0.65, the reaction temperature is 75-100 ℃ and the reaction time is 0.5-3h, after the reaction is finished, filtering to obtain a vanadium precipitation filter cake, pulping and washing the filter cake with deionized water, and then drying;
(2) Dissolving the dried product in the step (1) in a sodium hydroxide solution, controlling the final pH value to be between 10.5 and 12, stirring and reacting for 3 to 12 hours at the temperature of 90 to 100 ℃, filtering to obtain a filter cake and a colorless vanadium solution, and adding a second ammonium salt into the colorless vanadium solution, wherein the pH value is controlled to be between 90 and 100 ℃, and the weight ratio is as follows: the ammonium addition coefficient of m (V) is 0.65-1, the reaction is carried out for 0.5-3h, the white solid is obtained by filtering, washing and drying after the reaction is finished, the white solid is roasted for 1-3h at the temperature of 450-600 ℃ to obtain vanadium pentoxide,
Wherein the sodium vanadium solution is vanadium leaching solution obtained by roasting vanadium slag generated in the smelting process of vanadium titano-magnetite through sodium treatment and leaching with deionized water, wherein K is 0.241g/L, na-49.66g/L, si-1.18g/L, cr-2.15g/L and TV is 43.22g/L.
2. The method of claim 1, wherein in step (1), the added acid is sulfuric acid.
3. The method according to claim 1 or 2, wherein in step (1), the reducing agent is at least one of a vanadium-containing reducing agent, a sulfur-containing reducing agent, and an organic reducing agent.
4. A method according to claim 3, wherein the vanadium-containing reducing agent is selected from vanadyl sulfate, vanadium trichloride, vanadyl oxalate, vanadium dioxide, vanadium tetraoxide or vanadium trioxide.
5. A method according to claim 3, characterized in that the sulfur-containing reducing agent is selected from sulfur dioxide, sulfurous acid, sodium sulfite, sodium metabisulfite, sodium thiosulfate, hydrogen sulfide, sodium sulfide or sodium hydrosulfide.
6. A method according to claim 3, wherein the organic reducing agent is selected from vitamin C, oxalic acid, formic acid, tartaric acid or citric acid.
7. A method according to claim 3, wherein the reducing agent is at least one of vanadyl sulfate, sodium sulfite, and sodium metabisulfite.
8. The method of claim 1, wherein the first ammonium salt and the second ammonium salt are the same or different, and the first ammonium salt and the second ammonium salt are each independently selected from ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium chloride, monoammonium phosphate, or aqueous ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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