CN101381818B - Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash - Google Patents
Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash Download PDFInfo
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- CN101381818B CN101381818B CN2008101211610A CN200810121161A CN101381818B CN 101381818 B CN101381818 B CN 101381818B CN 2008101211610 A CN2008101211610 A CN 2008101211610A CN 200810121161 A CN200810121161 A CN 200810121161A CN 101381818 B CN101381818 B CN 101381818B
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- vanadium
- intermediate salt
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 107
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 150000003839 salts Chemical class 0.000 title claims abstract description 95
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000605 extraction Methods 0.000 title claims abstract description 36
- 239000002253 acid Substances 0.000 title claims abstract description 34
- 238000002386 leaching Methods 0.000 title claims abstract description 29
- 239000004575 stone Substances 0.000 title claims abstract description 8
- 239000010883 coal ash Substances 0.000 title claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000000706 filtrate Substances 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000012452 mother liquor Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002893 slag Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002956 ash Substances 0.000 claims description 22
- 238000005554 pickling Methods 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 11
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 claims description 10
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 229910001777 tschermigite Inorganic materials 0.000 abstract description 31
- 239000003245 coal Substances 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000011978 dissolution method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 239000010891 toxic waste Substances 0.000 abstract 1
- 239000010959 steel Substances 0.000 description 25
- 229910000831 Steel Inorganic materials 0.000 description 24
- 239000012074 organic phase Substances 0.000 description 19
- 210000000988 bone and bone Anatomy 0.000 description 18
- 238000000197 pyrolysis Methods 0.000 description 15
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 14
- 239000001117 sulphuric acid Substances 0.000 description 11
- 235000011149 sulphuric acid Nutrition 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000010445 mica Substances 0.000 description 6
- 229910052618 mica group Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- MCPTUMJSKDUTAQ-UHFFFAOYSA-N vanadium;hydrate Chemical compound O.[V] MCPTUMJSKDUTAQ-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 5
- 229940116357 potassium thiocyanate Drugs 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 4
- 230000009615 deamination Effects 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
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- 239000004615 ingredient Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 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 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QKDGGEBMABOMMW-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] QKDGGEBMABOMMW-UHFFFAOYSA-I 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
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- 238000005137 deposition process Methods 0.000 description 1
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- 235000021321 essential mineral Nutrition 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a preparation dissolution method for intermediate salt during the process of acid leaching extraction of vanadium pentoxide from vanadium-containing stone coal clinker. The method comprises the following steps: the vanadium-containing stone coal clinker undergoes acid leaching, so as to obtain an acid leaching solution; ammonium sulfate is added into the acid leaching solution to separate out tschermigite, so as to obtain a vanadium-bearing mother liquor as a raw material; the vanadium-containing mother liquor and iron elementary substance are added into a reaction vessel, wherein the mass of the iron elementary substance is 1 to 60 percent of that of the vanadium pentoxide in the vanadium-containing mother liquor; the mixture is stirred for full reaction, and is heated, evaporated and concentrated until the concentration of H<+> in the solution is between 18 and 22 mol per liter; after complete crystallization, the solution is cooled to the room temperature, and filtrate and filter residue are obtained through filtration; and the filter residue is taken, and intermediate salt solid is obtained. The method has the advantages that the method is simple; the operating environment is good; the whole process undergoes full-liquid phase operation; no pollution of toxic waste gas exists; more than 98 percent of vanadium in the mother liquor is enriched into theintermediate salt, thereby greatly simplifying the subsequent extraction operation; and a residual acid after preparation of the intermediate salt can be recovered, thereby greatly reducing the cost.
Description
(1) technical field
The present invention relates to a kind of preparation and dissolving method that contains intermediate salt in the scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process.
(2) background technology
Vanadium is a kind of important strategic goods and materials.The mankind just had been found that v element before 160 years, but just began to be applied on the industrial production up to 20 beginnings of the century.The pure metal vanadium is silver gray, has good ductility and erosion resistance.The product category of vanadium is various, and metallurgic products such as existing high purity vanadium metal, vanadium iron, vananum, vanadium carbide and vanadium carbonitride also have Vanadium Pentoxide in FLAKES, ammonium meta-vanadate, Chemicals such as potassium vanadate, vanadic acid sodium, vanadium hydroxide and vanadium chloride.Because vanadium has high-melting-point and easy deformation machining characteristics, is widely used in fields such as Iron And Steel Industry, national defence sophisticated technology, chemical industry and light and textile industries.Wherein the most important thing is to do the interpolation element in the steel and alloy, make chemical industry effective catalyst, activator.The vanadium steel that contains vanadium additive has very high hardness, wear resistance and bears the loading of large impact power, and has higher yield-point and plasticity-, is the main raw material(s) of automobile, aviation, machine manufacturing and transportation by railroad.
According to reports, the consumption iron and steel of vanadium accounts for 85% in the world, and non-ferrous metal accounts for 4%, and chemical industry and pottery account for 3%, and cast iron accounts for 1%, and other accounts for 2%.Therefore, influencing the supply and demand of vanadium and the factor of market value mainly is the production of iron and steel and vanadium alloy.When the production of Iron and Steel Production boom, particularly steel alloy increases substantially.The consumption of vanadium and international market price also increase gradually.At present, the China of potential consumption big country, the application of vanadium in steel is far below developed country, and this and China are that the status of production and consumption big country is unbecoming.Recent years, this gap is dwindled, and we can say that the application market of Chinese vanadium and DEVELOPMENT PROSPECT will be good.
Vanadium is aboundresources, widely distributed metallic element in the world, and content is 0.015% in the earth's crust, can be but do not have separately for the rich ore of exploitation, and always with low-grade and other mineral paragenesis.Vanadium titano-magnetite and bone coal are the main raw materials of vanadium extraction, and the main raw material(s) of the vanadium of countries in the world production at present is the vanadium slag and the bone coal of vanadium titano-magnetite by-product in smelting process, and China is as the same.
In the v-ti magnetite ore resources of China, V
2O
5Total reserves be 1741.28 ten thousand tons, wherein Panzhihua Region has 1,600 ten thousand tons, accounts for V in the national vanadium titano-magnetite
2O
5More than 90% of total reserves.
Bone coal is a kind of carbonaceous shale that contains, and is the black caustobiolith that forms under reducing environment, belongs to the high sapanthracite of metamorphic grade more, is the shallow-sea facies settling.Its main characteristic is the ash height, and density is big, and thermal value is low, compact structure, and the point of ignition height, nonflammable and be difficult to perfect combustion.In China, bone coal is mainly composed and is stored in down in the Cambrian stratum, forms outside the material desilt, silicon of bone coal, the inorganic salt composition such as calcareous, and organic part mainly is the low forms of life, sponge and the still indefinite original animals and plants of some classification such as algae.Because the source difference of yeath land leftover in deposition process, complexing, the adsorption of matter planted in the corruption that formation condition of the low forms of life such as phycomycetes or putrescible phycomycetes produce, and the influences such as hydrothermal solution dip-dye of diagenesis, contain in the bone coal or compose the associated element that has collected more, as kind surplus vanadium, aluminium, iron, magnesium, calcium, nickel, molybdenum, uranium, copper, selenium, gallium, trowel and the precious metal etc. 60.In some layer position, one or more associated elements reach industry mining grade or cut-off grade separately, can be used as certain mineral wealth and exploit separately, and reclaim valuable component by smelting.
China is that unexpected the discovery has vanadium in the bone coal when generally investigating phosphorus ore the end of the fifties, and reserves are very abundant.Claim according to " southern bone coal resource comprehensive investigation report ": the total reserves of 10 provinces such as Hunan, Hubei, Zhejiang, Guangdong, Guangxi, Guizhou, Anhui, Henan, Shaanxi, autonomous region's bone coal resource is 618.8 hundred million tons, wherein proven reserve are 39.0 hundred million tons, and combining and examining reserves is 579.8 hundred million tons.Only in the bone coal ore deposit of 7 provinces such as Hunan, Hubei, Jiangxi, Zhejiang, Anhui, Guizhou, Shaanxi, V
2O
5Reserves just reach 11,797 ten thousand tons.W (V wherein
2O
5) 0.50% reserves are 7705.5 ten thousand tons, are V in China's vanadium titano-magnetite
2O
56.7 times of total reserves surpass the total reserves of other various countries' vanadium of the world.Found in provinces and regions such as Xinjiang, Gansu also in recent years that reserves contained the scherbinaite coal than horn of plenty.
In the bone coal differ greatly in the grade various places of vanadium, is generally 0.13～1.00%, with regard to nationwide, in the bone coal grade of vanadium on average be lower than 0.5% account for 60%.V in the bone coal
2O
5Average grade and occupation rate see Table 1.
Table 1: the average grade of vanadium and occupation rate in the bone coal
| W(V 2O 5)％ | <0.1 | 0.1～0.3 | 0.3～0.5 | 0.5～1 | >1 |
| Occupation rate % | 3.1 | 23.7 | 33.6 | 33.8 | 2.8 |
The mineral composition of research bone coal shows: quartz is the essential mineral that constitutes bone coal, secondly is carbonaceous and clay mineral (kaolinite, mica mineral etc.), also has pyrite, garnet mineral and rhombspar etc.Other are a small amount of or trace quantity mineral is of a great variety, and various places are different.Vanadium in the bone coal is mainly composed in the mica minerals such as being stored in roscoelite, hydromica, biotite, white mica and illite, secondly is to compose to be stored in the mineral of other types such as some organic carbonaceous and ettringite garnet.
At present, China's process for extracting vanadium from stone coal mainly contains: sodium-salt calcination vanadium extraction, lime mud roasting vanadium extraction, calcium salt roasting vanadium extraction, wet method vanadium extraction, bone coal are directly acid-leaching vanadium-extracted etc.
Contain scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES at present and get pickling liquor to contain scherbinaite coal ash slag through acidleach usually, adding ammonium sulfate again, to separate out the vanadium mother liquid that contains that obtains behind the tschermigite be the feedstock production intermediate salt, in preparation method's technology of existing intermediate salt, mostly be to contain the vitriol that the vanadium mother liquid evaporation concentration obtains vanadium, vitriol is put in the calcining furnace and is calcined, and vanadium, low price iron are oxidized to V at a low price
2O
5And Fe
2O
3, the product after the calcining through leaching, obtains containing vanadium solution and Fe again
2O
3Throw out contains vanadium solution again through purification steps such as extraction, reextraction, obtains described V
2O
5This method for preparing intermediate salt needs high-temperature calcination, and energy consumption is big.
(3) summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation and dissolving method that contains intermediate salt in the scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process is provided.
The technical solution used in the present invention is:
A kind of preparation and dissolving method that contains intermediate salt in the scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process, described method comprises: get pickling liquor to contain scherbinaite coal ash slag through acidleach, adding ammonium sulfate again, to separate out the vanadium mother liquid that contains that obtains behind the tschermigite be raw material, in reaction vessel, add and contain vanadium mother liquid and iron simple substance, iron simple substance quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirring makes abundant reaction, and heating evaporation is concentrated into H in the solution
+Concentration is 18～22mol/L, and the complete postcooling of crystallization filters to get filtrate and filter residue to room temperature, gets filter residue, obtains the intermediate salt solid.
Intermediate salt preparation of the present invention is to add iron simple substance, to contain vanadium enrichment in the vanadium mother liquid in the intermediate salt crystal, reduce follow-up operation element amount and the consumption that extracts workshop section significantly, make a large amount of spent acid in the solution turn back to step (1) reuse simultaneously, to reduce the acid consumption significantly, and, saved the energy owing to saved the high-temperature calcination process.Intermediate salt is carried out X-ray diffraction analysis show, wherein contain ferric ammonium sulfate NH
4Fe (SO4)
2, Vanadosulfuric acid ammonium NH
4V (SO
4)
2, potassium aluminium sulfate KAl (SO
4)
2, exsiccated ammonium alum NH
4Al (SO
4)
2, Vanadosulfuric acid potassium KV (SO
4)
2, ammonium poly-vanadate (NH
4)
2V
6O
161.5H
2O, vanadic acid calcium CaV
2O
6Or the like, it is a kind of mixing salt of complexity, content of vanadium is with V in the intermediate salt
2O
5Meter can reach 4～8%, promptly from lime-ash V
2O
5Content 1～1.5% enrichment several times, the collection stoste V that intermediate salt dissolving is made
2O
5Concentration can reach more than the 10g/L, and this has just simplified subsequent operations process and raw material consumption greatly.
Described intermediate salt solid is further made intermediate salt dissolving clear liquid; Described intermediate salt dissolving clear liquid preparation method is as follows: add intermediate salt solid and water in reaction vessel, the add-on of water is 1.5～4L/kg intermediate salt solid, is warming up to 80～100 ℃ of stirring and dissolving 1.5～4 hours, filters to get filtrate and filter residue, get filtrate, obtain intermediate salt dissolving clear liquid.Described intermediate salt dissolving clear liquid further can prepare collection stoste, and collection stoste finally can obtain the Vanadium Pentoxide in FLAKES product again through extraction, reextraction, oxidation precipitation, ammonium poly-vanadate pyrolysis.
Common, process with described intermediate salt dissolving clear liquid preparation collection stoste is as follows: the adding intermediate salt is dissolved clear liquid in reaction vessel, stirs to add reductive agent down, extremely uses the potassium thiocyanate indicator to measure till the solution nondiscoloration, being neutralized to the pH value with alkaline solution is 1.8～3.0, obtains the stoste of coming together; Described reductive agent is the common reductive agent that is used for the Vanadium Pentoxide in FLAKES preparation in this area, is preferably Sulfothiorine or iron.
Concrete, described method can be as follows:
(1) acidleach: in reaction vessel, add strong acid solution and contain scherbinaite coal ash slag, H in the described strong acid solution
+Concentration be 8～12mol/L, the quality of described strong acid solution is that 2～3L/kg contains scherbinaite coal ash slag, is heated to 80～120 ℃ of dippings 3～9 hours, filters, and gets filtrate A, obtains acid solution; Concrete, the described scherbinaite coal ash slag that contains is to contain the lime-ash that the scherbinaite coal is discharged behind circulating fluidized bed combustion decarburization power generation and heat supply; Described strong acid is the common strong acid that is used for the Vanadium Pentoxide in FLAKES preparation in this area, as sulfuric acid, hydrochloric acid etc., is preferably sulfuric acid.
(2) tschermigite is produced: add pickling liquor and ammonium sulfate in reaction vessel, ammonium sulfate quality addition be in the pickling liquor 1.3～2 times of the aluminium sesquioxide quality (in the pickling liquor aluminium sesquioxide content after measured after, accurate calculation ammonium sulfate addition), stir, be cooled to 5～40 ℃, crystallization and separate out the tschermigite crystal, filter, filter residue B is thick tschermigite, and liquor B is for containing vanadium mother liquid; Thick tschermigite can obtain the smart tschermigite byproduct of high purity through adding the water heating for dissolving, filtering and remove impurity, recrystallization; Contain compound impurity such as the aluminium that leached simultaneously, iron in the pickling liquor that acidleach workshop section obtains, particularly a large amount of aluminium sesquioxides generates Tai-Ace S 150 with sulfuric acid reaction, and it will and extract workshop section to the subsequent preparation intermediate salt and have a negative impact.This step purpose is the Tai-Ace S 150 of removing substantially in the pickling liquor, produces the byproduct tschermigite, reclaims the bauxite resource in the lime-ash;
(3) intermediate salt preparation: add in reaction vessel and contain vanadium mother liquid and iron simple substance, iron simple substance quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirs and makes abundant reaction, and heating evaporation is concentrated into H in the solution
+Concentration is 18～221mol/L, and the complete postcooling of crystallization is to room temperature, and filter to get filtrate C and filter residue C get filter residue C, obtain the intermediate salt solid; Liquor C can be back to step (1);
(4) intermediate salt dissolving: in reaction vessel, add intermediate salt solid and water, the add-on of water is 1.5～4L/kg intermediate salt solid, is warming up to 80～100 ℃ of stirring and dissolving 1.5～4 hours, and D and filter residue D filter to get filtrate, get filtrate D, obtain intermediate salt dissolving clear liquid.Filter residue D can be back to step (1);
More specifically, described method is as follows:
(1) acidleach: add 4～6mol/L sulphuric acid soln and contain scherbinaite coal ash slag in reaction vessel, the sulphuric acid soln consumption is that 2～3L/kg contains scherbinaite coal ash slag, is heated to 80～120 ℃ of dippings 3～9 hours, filters and washing, gets filtrate A, is pickling liquor;
(2) tschermigite is produced: add pickling liquor and ammonium sulfate in reaction vessel, ammonium sulfate quality addition is 1.3～2 times of aluminium sesquioxide quality in the pickling liquor, stirs, crystallization separates out the tschermigite crystal, filter, get liquor B and filter residue B, filter residue B is thick tschermigite, and liquor B is for containing vanadium mother liquid;
(3) intermediate salt preparation: add in reaction vessel and contain vanadium mother liquid and iron powder, the iron powder quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirs and makes abundant reaction, and heating evaporation is concentrated into H in the solution
+Concentration is 18～22mol/L, and the complete postcooling of crystallization is to room temperature, and filter to get filtrate C and filter residue C get filter residue C and be the intermediate salt solid, and liquor C reclaims the sulphuric acid soln preparation that is applied to step (1);
(4) intermediate salt dissolving: in reaction vessel, add intermediate salt solid and water, the add-on of water is 1.5～4L/kg intermediate salt solid, be warming up to 80～100 ℃ of stirring and dissolving 2～4 hours, D and filter residue D filter to get filtrate, get filtrate D and be intermediate salt dissolving clear liquid, filter residue D reclaims and contains the vanadium ash components as step (1).
Utilizing the inventive method to make intermediate salt dissolving clear liquid, to prepare the step of Vanadium Pentoxide in FLAKES as follows:
1) collection stoste preparation: adding intermediate salt dissolving clear liquid in reaction vessel, stirring adds Sulfothiorine or iron powder reducing agent down, and extremely with till the nondiscoloration of potassium thiocyanate indicator mensuration solution, being neutralized to the pH value with ammoniacal liquor is 1.8～3.0, and stoste obtains coming together;
2) extraction: the collection stoste and the organic extractant that add volume ratio and be 1:1 in reaction vessel carry out extracting operation, separate organic phase and water, obtain containing vanadium organic phase and raffinate, described organic extractant is the mixture of 2-ethylhexyl phosphoric acid, tributyl phosphate and sulfonated kerosene volume ratio 10:5:85, and described extraction progression is 3～5 grades;
3) strip: adding volume ratio in reaction vessel is the sulphuric acid soln that contains vanadium organic phase and concentration 1.25～1.75mol/L of 5～10:1, strips, and water phase separated and organic phase obtain containing the vanadium water, and described extraction progression is 3～5 grades;
4) oxidation precipitation: in reaction vessel, add and contain the vanadium water, 50～60 ℃ of stirrings add sodium chlorate to solution down and are become by blueness till the yellow, and the ammoniacal liquor adjust pH was 1.9～2.5, in 90～100 ℃ of following precipitations 2～4 hours, cooling, crystallization, filtration, dehydration obtain the ammonium poly-vanadate crystal;
5) ammonium poly-vanadate pyrolysis: ammonium poly-vanadate crystal pyrolysis deamination obtains Vanadium Pentoxide in FLAKES.
The beneficial effect of the inventive method is mainly reflected in:
1, method is simple, and all processing units can all use homemade; Good operational environment, labour intensity is low, mechanization degree height, advanced technology, labour productivity height.
2, the full liquid-phase operation of whole process, no poisonous fume pollutes; Processing wastewater, waste liquid fully recovering, environmental friendliness.
3, technico-economical comparison advanced person, the resource recovery height.Vanadium in the mother liquor is enriched to more than 98% in the intermediate salt, and follow-up extracting operation is simplified greatly.
But 4, the spent acid reuse after the system intermediate salt, contain that vanadium mother liquid is not made intermediate salt and direct extraction phase ratio with system behind the tschermigite, sour consumption can reduce more than 50%, the alkali lye consumption when having reduced simultaneously preparation collection stoste significantly, thereby simplify the operation greatly, reduce cost significantly.
(4) description of drawings
Fig. 1 is for containing scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process flow sheet, and wherein frame of broken lines inside is divided into intermediate salt and comes together former liquid and preparation method thereof.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Thermal Power Engineering institute of Zhejiang University, the direct acid leaching extraction V of intermediate salt method stone coal ash
2O
5Pilot plant (comprises the acidleach glassed steel reaction vessels, tschermigite is produced glassed steel reaction vessels, intermediate salt evaporation glassed steel reaction vessels, intermediate salt dissolving glassed steel reaction vessels, collection stoste prepares glassed steel reaction vessels, the tower extractor of synthetic glass, the tower stripper of synthetic glass, oxidation precipitation glassed steel reaction vessels and ammonium poly-vanadate electricity pyrolysis oven), contain vanadium lime-ash processing power 800kg/d, end slag and the dedusting ash of used lime-ash for after circulating fluidized bed combustion, discharging, press slag 25% at the bottom of the mass ratio, dedusting ash 75%, mix the back as the lime-ash raw material, its chemical ingredients is: V
2O
51.26%, SiO
261.83%, Fe
2O
36.90%, Al
2O
316.58%, CaO0.30%, MgO1.31%.The occurrence status analysis revealed of vanadium in the lime-ash, most of vanadium is composed and is stored in the MICA, belongs to the difficult ore deposit of leaching.
The processing condition and the parameter thereof of pilot plant operation:
Acidleach: 100～110 ℃ of temperature, sulfuric acid concentration 4～5mol/L, leaching time 4～6h, liquid-solid ratio 3 (being that the sulphuric acid soln consumption is that 3L/kg contains scherbinaite coal ash slag);
Tschermigite is produced: it is 1.8 times of aluminium sesquioxide quality in the pickling liquor that ammonium sulfate adds quality, stirs and is cooled to room temperature;
Intermediate salt preparation: the vanadium mother liquid of producing behind the tschermigite that contains adds the iron powder quality for containing V in the vanadium mother liquid in the intermediate salt evaporating kettle
2O
530% of quality, the stirring heating evaporation concentration is to H
+Concentration 19～21mol/L, the complete postcooling of crystallization obtain intermediate salt solid V to room temperature after the vacuum filtration
2O
5Mass content is 4.8～8%, V in the filtrate
2O
5Only be 0.05g/l, the intermediate salt percent crystallization in massecuite reaches 98.8%;
The intermediate salt dissolving: in the intermediate salt dissolution kettle, add the intermediate salt solid, the stirring at normal temperature water dissolution, liquid-solid ratio 4,90～100 ℃ of solvent temperatures, dissolution time 4h, the intermediate salt dissolution rate reaches 99%;
Collection stoste preparation: in collection stoste preparation still, make reductive agent with iron powder, add-on till the solution nondiscoloration, is neutralized to pH2.5～3.0 with ammoniacal liquor, V in the collection stoste that makes with the potassium thiocyanate indicator
2O
5Concentration is 11g/L.
Extraction is stripped: the organic phase proportioning is P
204, TPB and sulfonated kerosene volume ratio be 10:5:85, organic phase: the water volume ratio is 1:1, the extraction of adverse current level Four, normal temperature; Reverse-extraction agent is a sulphuric acid soln, concentration 1.5mol/L, load organic phases: reverse-extraction agent volume ratio=10:1, four-stage counter-current back extraction, normal temperature;
The oxidation precipitation: add under 50～60 ℃ of heated and stirred of temperature till the sodium chlorate oxygenant makes solution become yellow by blueness, regulating pH with ammoniacal liquor is 2～2.3,95～100 ℃ of precipitation temperature, 3 hours precipitation time;
The pyrolysis deamination: 500～550 ℃ of pyrolysis temperatures obtain powdery V
2O
5
The key technical indexes that the pilot plant operation reaches:
The acid leaching efficiency of vanadium: 〉=85%;
The detersive efficiency of vanadium: 〉=95%;
Level Four extraction efficiency: 〉=99%;
Level Four reextraction efficient: 〉=99%;
Precipitation yield: 〉=98%;
Pyrolysis yield: 〉=98%;
The total recovery of vanadium: 〉=75%;
The by-product tschermigite:〉80kg/kgV
2O
5
V
2O
5Purity: 98.2%.
Embodiment 2:
The used scherbinaite coal ash slag that contains is the end slag and the dedusting ash of discharging after circulating fluidized bed combustion, press slag 25% at the bottom of the mass ratio, and dedusting ash 75% is mixed afterwards as the lime-ash raw material, and its chemical ingredients is: V
2O
51.26%, SiO
261.83%, Fe
2O
36.90%, Al
2O
316.58%, CaO0.30%, MgO1.31%.The occurrence status analysis revealed of vanadium in the lime-ash, most of vanadium is composed and is stored in the MICA, belongs to the difficult ore deposit of leaching.
The Vanadium Pentoxide in FLAKES extraction step is as follows:
(1) acidleach: add 5mol/L sulphuric acid soln 1590L and contain scherbinaite coal ash slag 533kg in the acidleach glassed steel reaction vessels, be heated to 110～115 ℃ of dippings 4 hours, filter and washing, get filtrate, obtain pickling liquor, the residue butt contains V
2O
50.26% (w/w); Residue can be delivered to the slag field and be used for the material of construction comprehensive utilization;
(2) tschermigite is produced: produce adding pickling liquor 2057L (recording wherein, aluminium sesquioxide content is 63kg) and ammonium sulfate 113kg in the glassed steel reaction vessels at tschermigite, stir, be cooled to room temperature, the tschermigite crystal is separated out in crystallization, vacuum filtration, getting filter residue is thick tschermigite 458kg, gets filtrate for containing vanadium mother liquid 1937L; Thick tschermigite is removed impurity, recrystallization through heat of solution, filtration, can obtain the smart tschermigite byproduct of high purity;
(3) intermediate salt preparation: add in intermediate salt evaporation glassed steel reaction vessels and contain vanadium mother liquid 1715L (recording wherein, pentoxide content is 4.785kg) and waste iron filing 1.44kg, the stirring heating evaporation concentration is to H
+Concentration 19～21mol/L, the complete postcooling of crystallization cross the leaching filter residue to room temperature, obtain intermediate salt solid 115kg, and the intermediate salt butt contains Vanadium Pentoxide in FLAKES 4.55%;
(4) intermediate salt dissolving: in intermediate salt dissolving glassed steel reaction vessels, add intermediate salt solid 115kg and water 460L, be warming up to 90～95 ℃, stirring and dissolving 4 hours is crossed leaching filtrate, obtain intermediate salt dissolving clear liquid 300L, clear liquid pentoxide content 13.52g/L;
(5) collection stoste prepares: prepare in collection stoste and add step (4) intermediate salt dissolving clear liquid in the glassed steel reaction vessels, stir adding reductive agent iron powder down, extremely use the potassium thiocyanate indicator to measure till the solution nondiscoloration, being neutralized to the pH value with ammoniacal liquor is 2.6, obtain the stoste of coming together, collection stoste V
2O
5Concentration is 13.12g/L;
(6) extraction: the collection stoste and the organic phase that add volume ratio and be 1:1 in the tower extractor of synthetic glass are carried out extracting operation, and extraction progression is 4 grades, separates organic phase and water, obtains containing vanadium organic phase and raffinate, and described organic phase is P
204, TBP and sulfonated kerosene volume ratio 10:5:85 mixture;
(7) strip: add in the tower stripper of synthetic glass and contain vanadium organic phase 200L and 1.5mol/L sulphuric acid soln 40L, strip, reextraction progression is 3 grades, and water phase separated and organic phase obtain containing the vanadium water;
(8) oxidation precipitation: in oxidation precipitation glassed steel reaction vessels, add and contain the vanadium water, 50～60 ℃ of stirrings add sodium chlorate to solution down and are become by blueness till the yellow, and the ammoniacal liquor adjust pH was 2.2, in 95～100 ℃ of following precipitations 4 hours, cooling, crystallization, filtration, dehydration obtain the ammonium poly-vanadate crystal;
(9) ammonium poly-vanadate pyrolysis: add the ammonium poly-vanadate crystal in ammonium poly-vanadate electricity pyrolysis oven, 500～550 ℃ of pyrolysis deaminations promptly get powdery V after the cooling
2O
5Product.
In this technological process: the acid leaching efficiency of vanadium is 85.20%; The detersive efficiency of vanadium is 96.21%; The level Four extraction efficiency is 99.35%; Three grades of reextraction efficient are 99.98%; The precipitation yield is 99.29%; The pyrolysis yield is 99.12%; The total recovery of vanadium is 80.11%; The by-product tschermigite is 81kg/kgV
2O
5V
2O
5Purity is 98.22%.
Embodiment 3:
The used scherbinaite coal ash slag that contains is the end slag and the dedusting ash of discharging after circulating fluidized bed combustion, press slag 25% at the bottom of the mass ratio, and dedusting ash 75% is mixed afterwards as the lime-ash raw material, and its chemical ingredients is: V
2O
51.26%, SiO
261.83%, Fe
2O
36.90%, Al
2O
316.58%, CaO0.30%, MgO1.31%.The occurrence status analysis revealed of vanadium in the lime-ash, most of vanadium is composed and is stored in the MICA, belongs to the difficult ore deposit of leaching.
The Vanadium Pentoxide in FLAKES extraction step is as follows:
(1) acidleach: in the acidleach glassed steel reaction vessels, add 5mol/L sulphuric acid soln 2364L (this sulphuric acid soln forms for high acidity filtrate and the initiate sulfuric acid mixed preparing that step 3 among the embodiment 2 obtains) and contain scherbinaite coal ash slag 788kg, be heated to 110～115 ℃ of dippings 4 hours, filter and washing, get filtrate, obtain pickling liquor, the residue butt contains V
2O
50.21%; Residue can be delivered to the slag field and be used for the material of construction comprehensive utilization;
(2) tschermigite is produced: produce adding pickling liquor 2458L (recording wherein, aluminium sesquioxide content is 82kg) and ammonium sulfate 124kg in the glassed steel reaction vessels at tschermigite, stir, be cooled to room temperature, the tschermigite crystal is separated out in crystallization, vacuum filtration, getting filter residue is thick tschermigite 752kg, gets filtrate for containing vanadium mother liquid 2330L; Thick tschermigite is removed impurity, recrystallization through heat of solution, filtration, can obtain the smart tschermigite byproduct of high purity;
(3) intermediate salt preparation: add in intermediate salt evaporation glassed steel reaction vessels and contain vanadium mother liquid 2330L (recording wherein, pentoxide content is 7.444kg) and waste iron filing 2.233kg, the stirring heating evaporation concentration is to H
+Concentration 19～21mol/L, the complete postcooling of crystallization cross the leaching filter residue to room temperature, obtain intermediate salt solid 137kg, and the intermediate salt butt contains Vanadium Pentoxide in FLAKES 6.23%;
(4) intermediate salt dissolving: in intermediate salt dissolving glassed steel reaction vessels, add intermediate salt solid 137kg and water 530L, be warming up to 90～95 ℃, stirring and dissolving 4 hours is crossed leaching filtrate, obtain intermediate salt dissolving clear liquid 353L, clear liquid pentoxide content 19.22g/L;
(5) collection stoste prepares: prepare in collection stoste and add step (4) intermediate salt dissolving clear liquid in the glassed steel reaction vessels, stir adding reductive agent iron powder down, extremely use the potassium thiocyanate indicator to measure till the solution nondiscoloration, being neutralized to the pH value with ammoniacal liquor is 2.6, obtain the stoste of coming together, collection stoste V
2O
5Concentration is 18.88g/L;
(6) extraction: the collection stoste and the organic phase that add volume ratio and be 1:1 in the tower extractor of synthetic glass are carried out extracting operation, and extraction progression is 4 grades, separates organic phase and water, obtains containing vanadium organic phase and raffinate, and described organic phase is P
204, TBP and sulfonated kerosene volume ratio 10:5:85 mixture;
(7) strip: add in the tower stripper of synthetic glass and contain vanadium organic phase 250L and 1.5mol/L sulphuric acid soln 60L, strip, reextraction progression is 3 grades, and water phase separated and organic phase obtain containing the vanadium water;
(8) oxidation precipitation: in oxidation precipitation glassed steel reaction vessels, add and contain the vanadium water, 50～60 ℃ of stirrings add sodium chlorate to solution down and are become by blueness till the yellow, and the ammoniacal liquor adjust pH was 2.2, in 95～100 ℃ of following precipitations 4 hours, cooling, crystallization, filtration, dehydration obtain the ammonium poly-vanadate crystal;
(9) ammonium poly-vanadate pyrolysis: add the ammonium poly-vanadate crystal at ammonium poly-vanadate electricity pyrolysis oven, 500～550 ℃ of pyrolysis deaminations promptly get powdery V after the cooling
2O
5Product.
In this technological process: the acid leaching efficiency of vanadium is 85.35%; The detersive efficiency of vanadium is 95.61%; The level Four extraction efficiency is 99.55%; Three grades of reextraction efficient are 99.95%; The precipitation yield is 99.16%; The pyrolysis yield is 98.92%; The total recovery of vanadium is 79.64%; The by-product tschermigite is 95kg/kgV
2O
5V
2O
5Purity is 98.42%.
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| CN102134649B (en) * | 2011-03-03 | 2013-01-23 | 东北大学 | Comprehensive utilization method for vanadium slag |
| CN102747225B (en) * | 2012-07-10 | 2013-08-07 | 中南大学 | Method for comprehensively recycling copper, selenium and uranium from stone coal extraction vanadic acid immersion liquid |
| CN102732736B (en) * | 2012-07-23 | 2015-01-14 | 中南大学 | Method for extracting vanadium from burning slag of stone coal vanadium mine fluidized bed |
| CN102912130A (en) * | 2012-11-13 | 2013-02-06 | 吉首大学 | Method for separating vanadium enriched in stone coal leaching solution |
| CN104046786B (en) * | 2013-10-15 | 2016-08-31 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method reclaiming metal from vanadium slag |
| CN104195330A (en) * | 2014-08-07 | 2014-12-10 | 西北有色地质研究院 | Technique for recovering crystals of aluminum potassium sulfate dodecahydrate in process of vanadium extraction via fly ash acid leaching |
| CN106399694A (en) * | 2016-10-08 | 2017-02-15 | 河钢股份有限公司承德分公司 | Method for synchronously extracting vanadium and aluminum from waste vanadium oxide smelter refractory brick |
| CN114350964B (en) * | 2021-11-30 | 2024-01-26 | 攀钢集团研究院有限公司 | Method for preparing vanadium pentoxide by utilizing high-phosphorus high-calcium vanadium slag and recycling leaching liquid |
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