CN108728649B - Method for resource utilization of stone coal acidic wastewater - Google Patents
Method for resource utilization of stone coal acidic wastewater Download PDFInfo
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- CN108728649B CN108728649B CN201810526596.7A CN201810526596A CN108728649B CN 108728649 B CN108728649 B CN 108728649B CN 201810526596 A CN201810526596 A CN 201810526596A CN 108728649 B CN108728649 B CN 108728649B
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- ammonium
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- 238000000034 method Methods 0.000 title claims abstract description 261
- 239000002351 wastewater Substances 0.000 title claims abstract description 113
- 239000003245 coal Substances 0.000 title claims abstract description 109
- 239000004575 stone Substances 0.000 title claims abstract description 109
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 72
- 150000003839 salts Chemical class 0.000 claims abstract description 122
- 229910052935 jarosite Inorganic materials 0.000 claims abstract description 97
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 82
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 79
- SVFOMDDAWOLOME-UHFFFAOYSA-N [N].[Mg] Chemical compound [N].[Mg] SVFOMDDAWOLOME-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000002500 ions Chemical class 0.000 claims abstract description 59
- 238000001556 precipitation Methods 0.000 claims abstract description 52
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 39
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 225
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 113
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 85
- 238000001704 evaporation Methods 0.000 claims description 76
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 60
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 57
- 229910052742 iron Inorganic materials 0.000 claims description 56
- 229910052720 vanadium Inorganic materials 0.000 claims description 56
- 238000002386 leaching Methods 0.000 claims description 53
- 230000008020 evaporation Effects 0.000 claims description 51
- 239000002244 precipitate Substances 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 38
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 38
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 34
- 239000012141 concentrate Substances 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 125000000524 functional group Chemical group 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 26
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 23
- 238000007792 addition Methods 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 23
- 239000011651 chromium Substances 0.000 claims description 23
- 239000003463 adsorbent Substances 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001099 ammonium carbonate Substances 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 19
- 229910052793 cadmium Inorganic materials 0.000 claims description 18
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 17
- 125000004122 cyclic group Chemical group 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 12
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 229920001429 chelating resin Polymers 0.000 claims description 9
- 235000014413 iron hydroxide Nutrition 0.000 claims description 9
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003337 fertilizer Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 244000005700 microbiome Species 0.000 claims description 5
- 235000010755 mineral Nutrition 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000012271 agricultural production Methods 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims 2
- 241000894007 species Species 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 30
- 238000006386 neutralization reaction Methods 0.000 abstract description 8
- 230000009615 deamination Effects 0.000 abstract description 7
- 238000006481 deamination reaction Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000706 filtrate Substances 0.000 description 85
- 238000001914 filtration Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 27
- 239000013078 crystal Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 13
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 239000013522 chelant Substances 0.000 description 5
- 229960004887 ferric hydroxide Drugs 0.000 description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052567 struvite Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical compound [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910001804 ammoniojarosite Inorganic materials 0.000 description 1
- 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 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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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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Abstract
The invention provides a method for recycling stone coal acidic wastewater, which comprises the steps of heavy metal recovery, salt enrichment, jarosite precipitation, evaporative crystallization of magnesium sulfate, crystallization of magnesium-nitrogen double salt, tail water circulation treatment and the like. According to the invention, heavy metal ions are separated and recovered from the stone coal acidic wastewater, and then the jarosite, magnesium sulfate and magnesium-nitrogen double salt are respectively obtained through a multi-step crystallization method, so that the high-efficiency separation and recovery of different components in the wastewater are realized, the problems that a large amount of waste residues and valuable components generated by a traditional wastewater neutralization and deamination method cannot be recovered are solved, various products with high added values are obtained, the product purity is high, no heavy metal is entrained, and the wastewater is returned to the technological process for recycling after treatment, so that the zero discharge of the wastewater is realized. The method has the advantages of low cost, simple operation, cleanness, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment and resource utilization, and relates to a method for resource utilization of stone coal acidic wastewater.
Background
The stone coal is one of the main raw materials for extracting vanadium, and besides vanadium, the stone coal also contains various associated elements such as aluminum, potassium, iron, calcium, magnesium, molybdenum, nickel, cobalt, copper, titanium, chromium, uranium, selenium and the like. The roasting-water leaching/acid leaching method and the direct acid leaching method are common vanadium extraction processes of stone coal, so that a large amount of acidic wastewater is generated by the processes. The use of additives in the roasting process, stripping agents/desorbing agents in the vanadium enrichment process, precipitating agents in the vanadium precipitation process and the leaching of various associated elements in the leaching process lead to the residue of a large amount of Na in the wastewater+、NH4 +、K+、Mg2+、V5+And other heavy metal elements, so that heavy metal removal, desalination and ammonia nitrogen removal treatment are required to realize the recycling of the wastewater and the recovery of components.
At present, the common treatment method of the stone coal acidic wastewater is a lime neutralization-ammonia blowing-distillation desalination method, most of high-valence vanadium and chromium are reduced to be low-valence by reduction treatment, lime is added for neutralization, at the moment, the vanadium, the chromium, the iron, the aluminum and other heavy metals in the solution form sulfate and hydroxide precipitates, a large amount of calcium sulfate precipitates are generated by the sulfate and the lime, alkaline solution enters an ammonia blowing process, ammonia is absorbed by sulfuric acid to recover ammonium sulfate, finally salt-containing wastewater is distilled to obtain mixed salt, and steam condensate water is recycled. CN 1899977A discloses a method for treating and utilizing tail water from vanadium extraction and precipitation of stone coal, namely, procedures of lime neutralization and ammonia blowing are adopted. The conventional method has the advantages of good heavy metal ion removal effect, simple operation, less equipment and the like, but ferric hydroxide and aluminum hydroxide generated in the neutralization and precipitation process have better flocculation effect and adsorb a large amount of wastewater and metal ions, so the neutralization and precipitation amount is very large, and the precipitate belongs to dangerous waste and cannot be directly buried due to the entrainment of polluted heavy metal ions; the energy consumption of the ammonia blowing and distillation desalting processes is high, and secondary atmospheric pollution is easily caused in the ammonia blowing process; in the whole process, only ammonium sulfate can be recovered in the deamination process, evaporation condensate water can be recovered in the distillation desalination process, and other parts of heavy metal, alkali metal and alkaline earth metal cannot be separated and recovered.
Because the energy consumption is higher in the single distillation desalination process, scaling is easy, the salt-containing wastewater is treated by adopting a combination method, CN 101759313A discloses a resource treatment method for stone coal vanadium extraction high-salinity heavy metal-rich wastewater, lime is added into the stone coal wastewater to neutralize and adjust alkali, soda is added to reduce the hardness of water, a flocculating agent is added to reduce the turbidity of the water, electrodialysis desalination treatment is carried out to obtain fresh water and concentrated water, the fresh water is reused in the stone coal vanadium extraction process, and the concentrated water is evaporated by adopting a four-effect low-temperature plate evaporator to obtain condensed water and industrial salt. CN 102642963A discloses a comprehensive treatment method for salt-containing wastewater from vanadium extraction from stone coal, which also adopts lime neutralization, soda ash hardness removal and flocculation precipitation for pretreatment, and then adopts reversed electrodialysis, reduced pressure membrane distillation and crystallization treatment in turn. Compared with a single distillation method, the process has lower energy consumption, but the membrane treatment such as electrodialysis still has the problems of higher requirement on water quality, easy membrane pollution, high cost of matched equipment and the like.
After heavy metal ions are removed from the stone coal wastewater, the cost of deamination and desalination is high by adopting the method, so that the chemical precipitation method, the crystallization method and the like are usually adopted to simplify the process and reduce the cost. Plum inspection et al (struvite precipitation method for treating low-concentration ammonia nitrogen wastewater from vanadium extraction from stone coal. industrial water treatment, 2010,30(9):35-38.) propose a method for removing ammonia nitrogen by generating struvite precipitate, adjust the pH value of wastewater, use magnesium chloride and disodium hydrogen phosphate as precipitating agents, control reaction conditions, generate struvite precipitate to reduce the ammonia nitrogen content in wastewater, meet the relevant national discharge standards, and the struvite precipitate can also be used as a compound fertilizer. CN 101343695A discloses a method for reducing the content of potassium and sodium in vanadium extraction leaching circulating liquid, which comprises the steps of firstly adjusting the solution to be acidic, heating and adding potassium and sodium removing agents containing iron ions, and controlling the pH value to carry out precipitation reaction. The chemical precipitation method and the crystallization method have low cost and less equipment investment, but only remove one kind of components in the wastewater, do not consider the integral composition of the wastewater, and do not effectively recycle valuable components.
In conclusion, the treatment of the stone coal acidic wastewater starts from integral composition, and various components in the wastewater are removed step by adopting a reasonable method, so that the cost of wastewater treatment can be reduced, and the valuable components can be recycled.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for recycling stone coal acidic wastewater. According to the invention, heavy metal ions are separated and recovered from the stone coal acidic wastewater, and then chemical components such as alkali metal, alkaline earth metal, ammonia nitrogen and the like are separated and recovered by adopting a multi-step crystallization method, so that various products with high added values are obtained, and the high-efficiency recycling of resources in the wastewater is realized while the wastewater is effectively treated; meanwhile, the process method has the advantages of low cost, simplicity in operation, cleanness, environmental friendliness and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for resource utilization of stone coal acidic wastewater, which comprises the following steps:
(1) recovering heavy metal ions in the stone coal acidic wastewater to obtain a heavy metal concentrate and a solution;
(2) enriching the solution obtained in the step (1), adding an iron-containing substance, and carrying out precipitation reaction to obtain jarosite precipitate and a solution;
(3) concentrating and crystallizing the solution obtained in the step (2) to obtain magnesium sulfate solid and solution;
(4) and (3) adding ammonium salt and/or ammonia water into the solution obtained in the step (3), crystallizing to obtain magnesium-nitrogen double salt and a solution, and returning the obtained solution to the step (1).
The invention mainly adopts a chemical method to realize resource utilization of the stone coal acidic wastewater, firstly separates and recovers heavy metal ions, and then realizes Mg by adding a reagent to form crystals2+、Na+、K+And NH4+And the separation and recovery of chemical components avoid the problems that a large amount of waste residues and valuable components generated by the traditional wastewater neutralization deamination method cannot be recovered, and the method has the advantages of low cost, simplicity in operation, cleanness, environmental friendliness and the like, and the wastewater is returned to the process for cyclic treatment after being treated so as to realize zero discharge of the wastewater.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
As the preferable technical scheme of the invention, the stone coal acidic wastewater in the step (1) is the wastewater of the process for extracting vanadium by a stone coal sulfuric acid method.
Preferably, the stone coal acid wastewater in the step (1) does not contain Cl－And F－。
In the invention, the stone coal acidic wastewater is wastewater generated after vanadium extraction from stone coal, and the stone coal does not contain Cl－And F－As long as no Cl is added in the process of acid leaching vanadium extraction－And F－Does not generate Cl－And F－The waste water and the prior clean vanadium extraction process also avoid Cl as much as possible－And F－The invention is used for treating the wastewater generated by the current clean production process.
Preferably, the pH of the stone coal acidic wastewater in the step (1) is less than 7, such as 6, 5, 4, 3, 2, 1, 0, -1 or-2, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 0 to 6.
Preferably, the heavy metal ion recovery in step (1) adopts an adsorption method or a precipitation method, preferably an adsorption method.
Preferably, the adsorbent used in the adsorption method is a chelating resin and/or a biological adsorbent.
Preferably, the functional group of the chelating resin includes any one of a nitrogen-containing functional group, a phosphorus-containing functional group, an oxygen-containing functional group, or a sulfur-containing functional group, or a combination of at least two thereof, as typical but non-limiting examples of the combination are: the functional group containing nitrogen and the functional group containing phosphorus are preferably a combination of the functional group containing nitrogen and the functional group containing sulfur, a combination of the functional group containing nitrogen, the functional group containing phosphorus and the functional group containing oxygen, a combination of the functional group containing phosphorus, the functional group containing oxygen and the functional group containing sulfur, and a combination of the functional group containing nitrogen, the functional group containing oxygen and the functional group containing sulfur.
Preferably, the biological adsorbent comprises any one of or a combination of at least two of natural organic adsorbents and modifications thereof, microorganisms and modifications thereof, or agricultural, forestry, animal husbandry and fishery waste and modifications thereof, and typical but non-limiting examples of the combination are: the combination of natural organic adsorbent and microorganism, the combination of natural organic adsorbent and modified substance thereof, the combination of microorganism and waste of agriculture, forestry, animal husbandry and fishery, the combination of natural organic adsorbent, microorganism and waste of agriculture, forestry, animal husbandry and fishery, and the like.
According to the invention, the adsorption method is preferentially adopted for recovering heavy metal elements, the used adsorbent can selectively recover heavy metals in the stone coal acidic wastewater, and alkali metals, alkaline earth metals and ammonia nitrogen can not be adsorbed, so that valuable single salt or double salt products of the alkali metals, the alkaline earth metals and the ammonia nitrogen can be conveniently purified and recovered by a crystallization method in the subsequent process, the problems that the process slag amount is large, a large amount of salt, ammonia nitrogen and unrecovered heavy metals are carried in mixed precipitates and the high-efficiency separation and recovery of valuable components in the wastewater can not be realized by the traditional neutralization and precipitation method are avoided.
Preferably, the precipitating agent used in the precipitation method is a sulfide.
Preferably, the sulphide comprises any one of sodium sulphide, potassium sulphide, ammonium sulphide, sodium hydrosulphide, potassium hydrosulphide or ammonium hydrosulphide, or a combination of at least two of these, typical but non-limiting examples being: combinations of sodium sulfide and potassium sulfide, sodium sulfide and sodium hydrosulfide, potassium sulfide and ammonium hydrosulfide, sodium sulfide, potassium sulfide and ammonium sulfide, sodium sulfide, potassium sulfide, sodium hydrosulfide and potassium hydrosulfide, and the like.
Preferably, the heavy metal concentrate of step (1) comprises a combination of at least two of vanadium, chromium, iron, cobalt, nickel, copper, zinc or cadmium, typical but non-limiting examples being: combinations of vanadium and chromium, combinations of copper and zinc, combinations of iron, cobalt and nickel, combinations of vanadium, chromium, iron and cobalt, combinations of cobalt, nickel, copper, zinc and cadmium, and the like.
Preferably, the concentrate of step (1) further comprises aluminum and arsenic.
In the invention, the heavy metal concentrate produced by the adsorption method or the precipitation method is separated and recovered according to the prior art, and the content of the residual heavy metal in the residual solution meets the national relevant sewage discharge standard. As arsenic is a common harmful element in the stone coal wastewater, the arsenic can be removed by an adsorption method; the aluminum ions have a strong flocculation property and are adsorbed and removed in the treatment process of the adsorption method or the precipitation method, so that the obtained enriched material also comprises aluminum and arsenic.
As a preferable technical scheme of the invention, the enrichment method in the step (2) comprises the step of returning to the stone coal leaching process for cyclic leaching or evaporative concentration, and preferably the step of returning to the stone coal leaching process for cyclic leaching.
In the invention, the stone coal leaching process does not belong to the process step in the stone coal acidic wastewater treatment method, but belongs to the process of generating the wastewater, namely the step in the stone coal vanadium extraction process.
Preferably, when the enrichment method in the step (2) is returned to the stone coal leaching process for cyclic leaching, the obtained high-concentration salt-containing solution contains Mg2+、Na+、K+And NH4 +。
Preferably, Mg in the high concentration salt-containing solution2+The concentration is 10 to 25g/L, for example, 10g/L, 12g/L, 15g/L, 16g/L, 18g/L, 20g/L, 22g/L or 25g/L, etc., but is not limited to the values listed, and other values not listed in the numerical range are also applicable, and 15 to 20g/L is preferable.
Preferably, the high concentration salt-containing solution contains Na+The concentration is not more than 150g/L, for example, 150g/L, 140g/L, 130g/L, 120g/L, 110g/L, 100g/L, 90g/L, 80g/L, 70g/L or 60g/L, etc., but is not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably not more than 130g/L, and more preferably not more than 90 g/L.
Preferably, K is in the high concentration salt-containing solution+The concentration is 70g/L or less, for example, 70g/L, 65g/L, 60g/L, 55g/L, 50g/L, 45g/L, 40g/L, 35g/L, 30g/L or 25g/L, but is not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 60g/L or less, and more preferably 55g/L or less.
Preferably, the high concentration salt-containing solution contains NH4 +The concentration is less than or equal to 40g/L, for example, 40g/L, 35g/L, 30g/L, 25g/L, 20g/L, 15g/L, 10g/L or 5g/L, but is not limited to the recited values, and other values not recited within the range are equally applicable, preferably less than or equal to 30 g/L.
In the invention, the acid wastewater after heavy metal recovery is returned to the stone coal leaching process for enriching salt, and Na in the cyclic leaching process is controlled+、K+、Mg2+And NH4 +The concentration of the vanadium is higher, so that the problem that the leaching rate of the vanadium is reduced due to the influence of the diffusion leaching of the vanadium and the entrainment loss of the formed vanadium caused by the generation of sulfate precipitates caused by overhigh ion concentration is avoided.
As a preferred technical scheme of the invention, the enrichment method in the step (2) is evaporation concentrationWhen a high-concentration salt-containing solution is obtained, which contains Mg2+、Na+、K+And NH4 +。
Preferably, Mg in the high concentration salt-containing solution2+The concentration is 10 to 60g/L, for example, 10g/L, 20g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, 55g/L or 60g/L, etc., but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, preferably 20 to 60g/L, and more preferably 30 to 60 g/L.
Preferably, the high concentration salt-containing solution contains Na+The concentration is 155g/L or less, for example 155g/L, 150g/L, 140g/L, 130g/L, 120g/L, 110g/L, 100g/L, 90g/L, 80g/L, 70g/L or 60g/L, etc., but is not limited to the values listed, and other values not listed within the numerical range are equally applicable, preferably 140g/L or less.
Preferably, K is in the high concentration salt-containing solution+The concentration is less than or equal to 105g/L, for example, 105g/L, 100g/L, 95g/L, 90g/L, 85g/L, 80g/L, 75g/L, 70g/L, 65g/L, 60g/L, etc., but is not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably less than or equal to 95 g/L.
Preferably, the high concentration salt-containing solution contains NH4 +The concentration is less than or equal to 90g/L, for example 90g/L, 80g/L, 70g/L, 65g/L, 60g/L, 55g/L, 50g/L or 45g/L, but is not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably less than or equal to 70 g/L.
In the invention, the circulation leaching process is adopted to enrich Na+、K+、Mg2+And NH4 +Compared with an evaporation concentration method, the ion evaporation method can reduce the evaporation amount of water and reduce energy consumption; the method can also avoid the phenomenon that the heavy metal content in the solution is too high due to direct evaporation and enrichment and enters the byproducts, and the concentrated solution is subjected to the step of selectively recovering the heavy metal each time by adopting a circulating leaching method, so that the subsequent byproducts do not contain the heavy metal.
At present, most of the acid leaching vanadium extraction processes of stone coal can carry out acid leaching on K in acid leaching solution+And Al3+Recovering to obtain potassium sodium sulfateAlum, supplement of NH4 +Can obtain ammonium alum, so when the waste water is circularly leached, K is+And NH4 +Because of the formation of crystals, the concentration of the crystals is not increased obviously and only Na is contained+And Mg2+Is enriched and Na is evaporated and concentrated+、K+、Mg2+And NH4 +Synchronously enriching; the former avoids evaporation of enriched K+And NH4 +The ions consume a large amount of iron-containing substances in the process of crystallizing jarosite, the obtained crystallized product basically does not contain jarosite and ammonioiarosite, mainly jarosite, and can be recycled independently, and the latter obtains a mixture of jarosite, ammonioiarosite and jarosite.
The above cyclic leaching process is not limited to K+、NH4 +And Al3+The ion is recovered by a process as long as the proper Na is obtained+、K+、Mg2+And NH4 +The ion concentration can be used for the next operation procedure, and the method is suitable for the acid wastewater obtained by different types of stone coal and different vanadium extraction methods.
As a preferred technical solution of the present invention, the iron-containing substance in step (2) includes any one or a combination of at least two of iron sulfate, iron chloride, iron nitrate, iron phosphate, iron hydroxide, iron oxide, iron-rich minerals or iron-rich tailings, and the combination is typically but not limited to: a combination of iron sulfate and iron hydroxide, a combination of iron hydroxide and iron oxide, a combination of an iron-rich mineral and an iron-rich tailings, a combination of iron sulfate, iron hydroxide and iron oxide, and the like, preferably any one or a combination of at least two of iron sulfate, iron hydroxide and iron oxide, and more preferably iron sulfate.
In the invention, the iron-containing substance is preferably ferric sulfate, ferric hydroxide or ferric oxide, namely, other anion components are not introduced into the system under the acidic condition, so that only sulfate precipitation can be obtained in the subsequent crystallization process.
Preferably, the iron-containing substance is added in an amount of 0.1 to 3 times, for example, 0.1 times, 0.3 times, 0.5 times, 0.8 times, 1 times, 1.2 times, 1.5 times, 2 times, 2.5 times or 3 times, the theoretical amount required for producing jarosite, but is not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 0.5 to 1.5 times, and more preferably 0.8 to 1 time.
Preferably, the composition of the jarosite is MFe3(SO4)2(OH)6Wherein M is Na+、NH4 +Or K+Any one or a combination of at least two of the following, typical but non-limiting examples being: na (Na)+And NH4 +Combination of (A) and (B), Na+And K+Combination of (A) and (B), Na+、NH4 +And K+Combinations of (a), (b), and the like.
In the present invention, alum refers to a double salt composed of two or more kinds of metal sulfates, and the addition of an iron-containing substance to generate an jarosite precipitate is because it is more likely to crystallize out of solution than the corresponding single salt, and can also form larger grains, which is advantageous for solid-liquid separation.
In the present invention, the theoretical amount of iron-containing material required to form jarosite is based on Na in solution+、NH4 +And K+Is calculated from the total amount of (c).
In a preferred embodiment of the present invention, the pH of the precipitation reaction in step (2) is-2 to 4, for example, -2, -1.5, -1, -0.5, 0, 0.5, 1, 1.5, 2, 3 or 4, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, preferably-1 to 3, and more preferably 0 to 1.3.
Preferably, the pH is adjusted with an acidic or basic substance.
In the present invention, the process of producing jarosite produces an acid having the formula 3Fe3++2SO4 2-+M++6H2O＝MFe3(SO4)2(OH)6+6H+Therefore, it is necessary to continuously adjust the pH of the solution so that the precipitation reaction is always performed within this pH range.
Preferably, the acidic substance comprises any one of hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, or a combination of at least two of these, typical but non-limiting examples being: a combination of hydrochloric acid and nitric acid, a combination of phosphoric acid and sulfuric acid, a combination of hydrochloric acid, phosphoric acid and sulfuric acid, and the like, with sulfuric acid being preferred.
Preferably, the basic substance comprises any one of sodium hydroxide, potassium hydroxide, aqueous ammonia, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate or a combination of at least two of them, typical but non-limiting examples being: a combination of sodium hydroxide and potassium hydroxide, a combination of sodium carbonate and potassium carbonate, a combination of sodium hydroxide, sodium carbonate and sodium bicarbonate, a combination of sodium hydroxide, potassium hydroxide and aqueous ammonia, and the like, and preferably any one of or a combination of at least two of sodium hydroxide, potassium hydroxide or aqueous ammonia.
In the invention, the pH value is preferably adjusted by sulfuric acid, sodium hydroxide, potassium hydroxide or ammonia water, and other components are not introduced into the system, so that only sulfate precipitate can be obtained in the subsequent crystallization process.
Preferably, the precipitation reaction in step (2) is carried out at a temperature of 30 to 200 ℃, for example, 30 ℃, 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃ or 200 ℃, but not limited to the recited values, and other values not recited in the above range are also applicable, preferably 60 to 150 ℃, and more preferably 101 to 150 ℃.
Preferably, the precipitation reaction time in step (2) is 0.2 to 8 hours, such as 0.2 hour, 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 0.5 to 6 hours, and more preferably 1 to 4 hours.
The method for separating and recovering Na by adopting the crystallized jarosite is adopted in the invention+、K+And NH4 +By controlling the adding amount of the iron-containing substances, the pH value of the solution, the precipitation temperature and other conditions, the jarosite precipitate with higher purity and the residual Na in the solution can be obtained+、K+And NH4 +Low concentration, meeting the requirement of subsequent process, Fe3+Substantially free of residual, Mg2+The concentration is kept unchanged during the process, and the concentration can be changedDirectly evaporating and crystallizing to prepare magnesium sulfate.
The invention adopts harsher reaction conditions to crystallize the jarosite, not only from the viewpoint of precipitating the jarosite, but also in order to avoid the entrainment loss of vanadium in the crystallization process, because the vanadium is cation under the pH condition, VO2 +Even at higher temperature, the iron vanadate precipitate can not be generated with iron, so that the high-temperature precipitation of the jarosite avoids the entrainment of vanadium, and the vanadium can enter the multi-metal concentrate.
Preferably, the jarosite precipitate of step (2) is used for recovery of valuable components or for landfill disposal.
Preferably, the jarosite precipitate is recovered to obtain an ammonium sulfate solution, iron oxide and an alkali metal sulfate solution.
In the invention, the method for recovering valuable components from the generated jarosite precipitate comprises the following steps: and recovering ammonia gas and sulfur trioxide generated by roasting the jarosite to obtain an ammonium sulfate solution, and washing the roasted material with water to obtain an iron oxide product and an alkali metal sulfate solution.
The ammonium sulfate solution can be used for a vanadium extraction process or for preparing the magnesium-nitrogen compound fertilizer in the step (4), the iron oxide product can be used for removing alkali metals in the step (2), and the alkali metal sulfate solution can be used for separating and recovering potassium and sodium according to the existing process.
According to the invention, the obtained jarosite through crystallization after cyclic leaching enrichment is relatively pure jarosite, so that iron oxide and sodium sulfate products can be directly recovered through a roasting-water washing method; the jarosite obtained by evaporation, concentration and enrichment is used as a mixture, ammonium sulfate, ferric oxide and a high-concentration potassium-sodium mixed salt solution are recovered by a roasting-water washing method, wherein the ammonium sulfate and the ferric oxide can be returned to the stone coal vanadium extraction process, and the potassium-sodium mixed salt solution basically does not contain ammonium radicals due to high deamination rate of the roasting method, and can be directly separated by methods such as crystallization to obtain potassium sulfate and sodium sulfate with high purity. In the traditional lime neutralization-deamination-distillation desalting method, because the deamination rate is not particularly high, ammonium radicals still remain in a potassium-sodium mixed salt solution after deamination, and a large amount of ammonium sulfate still remains in mixed salt obtained by final distillation desalting.
In the invention, the jarosite precipitate does not contain heavy metal, and can be directly buried after being washed and deacidified.
The method firstly recovers most heavy metals by adopting an adsorption method, adds insufficient iron-containing compounds into the subsequent jarosite precipitation, adopts harsher reaction conditions, and ensures that less Fe remains in the solution through theoretical analysis and experimental verification3+The jarosite has high crystallization purity and does not carry waste water components such as heavy metals, so valuable components can be selectively recycled or buried.
At present, the technology for removing the alkali metal-containing industrial wastewater in other industries also adopts the jarosite method, and in order to complete the reaction, a large amount of iron-containing compounds are added in the technology or the reaction is carried out at a lower temperature (less than or equal to 100 ℃), so that a large amount of Fe is contained in the wastewater3+Residual, the solution must be adjusted to a higher pH to remove Fe3+So that a large amount of precipitates are generated, which wastes resources, and the precipitates can not meet the requirements of common wastes and can not be directly buried because most of the precipitates are iron hydroxides which have good flocculation and carry wastewater and various components in the wastewater.
As a preferred embodiment of the present invention, the concentration in the step (3) is an evaporation treatment.
Preferably, the evaporation treatment is reduced pressure evaporation, and the degree of vacuum of the reduced pressure evaporation is 10 to 90kPa, for example, 10kPa, 20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 80kPa, or 90kPa, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the evaporation temperature is 60 to 100 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the evaporation treatment time is 0.2 to 6 hours, such as 0.2 hour, 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, NH in said solution after said evaporation treatment4 +The concentration is 70g/L or less, for example 70g/L, 65g/L, 60g/L, 55g/L, 50g/L, 45g/L, 40g/L, 35g/L or 30g/L, etc., but is not limited to the recited values, and other values not recited within the range are also applicable, preferably 50g/L or less.
Preferably, Na in the solution after the evaporation treatment+The concentration is 135g/L or less, for example 135g/L, 130g/L, 120g/L, 110g/L, 100g/L, 90g/L, 80g/L, 70g/L, 60g/L, 50g/L or 40g/L, etc., but is not limited to the recited values, and other values not recited within the range of values are also applicable, preferably 90g/L or less.
Preferably, K in the solution after the evaporation treatment+The concentration is 80g/L or less, for example 80g/L, 70g/L, 60g/L, 50g/L, 40g/L, 30g/L, 20g/L or 10g/L, etc., but is not limited to the recited values, and other values not recited within the range are also applicable, preferably 50g/L or less.
In the invention, Na in the evaporation concentrated solution is controlled and evaporated in the process of reduced pressure evaporation+、NH4 +And K+The concentration of the magnesium sulfate is reduced, so that the generated sulfate crystal is prevented from being separated out, and the magnesium sulfate byproduct with high purity can be obtained by evaporation and crystallization at a lower temperature (60-100 ℃). In addition, the process of evaporating and crystallizing the magnesium sulfate is carried out under an acidic condition, because the concentration of vanadium is increased in the process of evaporating and concentrating, and the vanadium exists in a cation form in a solution after the jarosite is generated by reaction (the pH is preferably 0-1.3), so that hydrolytic precipitation and entrainment loss caused by the hydrolytic precipitation can be avoided.
Preferably, the steam obtained by the evaporation treatment is condensed and then used in the stone coal vanadium extraction process.
As a preferred embodiment of the present invention, the ammonium salt in step (4) includes any one or a combination of at least two of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium bisulfate, ammonium carbonate or ammonium bicarbonate, and the combination is exemplified by, but not limited to: a combination of ammonium chloride and ammonium sulfate, a combination of ammonium sulfate and ammonium bisulfate, a combination of ammonium bisulfate and ammonium bicarbonate, a combination of ammonium chloride, ammonium sulfate and ammonium nitrate, a combination of ammonium sulfate, ammonium bisulfate, ammonium carbonate and ammonium bicarbonate, and the like, preferably any one or a combination of at least two of ammonium sulfate, ammonium bisulfate, ammonium carbonate or ammonium bicarbonate, and more preferably ammonium sulfate and/or ammonium bisulfate.
Preferably, the ammonium salt and/or the ammonia water in the step (4) are added in an amount of MgSO (MgSO) for generating the magnesium-nitrogen double salt4·(NH4)2SO4·6H2O is preferably 0 to 2.5 times, for example, 0, 0.2, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2 or 2.5 times the theoretical amount of O, but not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, preferably 0.2 to 1.2 times.
In the invention, the solution treated in the step (3) is saturated magnesium sulfate solution, and Mg is obtained after evaporation at the temperature of 60-100 DEG C2+The concentration is high (100 g/L-110 g/L) enough to generate magnesium-nitrogen double salt, so that ammonium salt and/or ammonia water are added at the time.
In a preferred embodiment of the present invention, the temperature of the crystallization in the step (4) is 0 to 100 ℃, for example, 0 ℃, 10 ℃,20 ℃,30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃ or 100 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are preferably 10 to 60 ℃ and more preferably 20 to 40 ℃.
Preferably, the magnesium-nitrogen double salt in the step (4) is used as a magnesium-nitrogen compound fertilizer.
Preferably, the magnesium nitrogen double salt in the step (4) is used for agricultural production and/or forestry production.
The invention adopts the method of crystallization to generate magnesium-nitrogen double salt to Mg2+Recovering Na from the system+、NH4 +、K+、Mg2+And SO4 2-Investigation of difference of crystallization regions and combination of low-temperature solubility ratio Na of magnesium-nitrogen double salt+、NH4 +And K+The sulfate has low solubility, so that the magnesium nitrogen complex with higher purity can be obtained by cooling and crystallizing in a proper temperature rangeThe magnesium content in the double salt is 6.7 wt%, the ammonium content is 10 wt%, and the double salt is suitable for being used as a magnesium-nitrogen composite slow release fertilizer in agricultural and forestry production.
In the invention, tail water is obtained after wastewater treatment, heavy metals in a tail water solution are enriched, and the concentration of residual ions is higher due to the operations such as concentration treatment and the like in the wastewater treatment process, so that the tail water can be returned to the process for cyclic treatment, and meanwhile, steam condensate water generated in the whole wastewater treatment process is used in the process of extracting vanadium from stone coal, thereby realizing zero discharge of wastewater and high-efficiency utilization of resources.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) recovering heavy metal ions in the stone coal acidic wastewater by adopting an adsorption method or a precipitation method to obtain a heavy metal concentrate and a solution;
(2) returning the solution obtained in the step (1) to a stone coal leaching process for cyclic leaching or evaporation concentration enrichment, adding an iron-containing substance, adjusting the pH value of the solution to-2-4, and carrying out precipitation reaction at 30-200 ℃ for 0.2-8 h to obtain jarosite precipitate and a solution;
(3) evaporating and crystallizing the solution obtained in the step (2), wherein the evaporation treatment vacuum degree is 10-90 kPa, the temperature is 60-100 ℃, and the time is 0.2-6 h, so as to obtain magnesium sulfate solid and solution;
(4) and (3) adding ammonium salt and/or ammonia water into the solution obtained in the step (3), crystallizing at the temperature of 0-100 ℃, separating to obtain magnesium-nitrogen double salt and the solution, and returning the obtained solution to the step (1) for circular treatment.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method is combined with the ion composition of a stone coal wastewater system, and adopts a multi-step crystallization method to respectively obtain the jarosite, the magnesium sulfate and the magnesium-nitrogen double salt, so that the high-efficiency separation of different components in the wastewater is realized, various products with high added values are obtained by recovery, the purity of byproducts is high, and no heavy metal is entrained;
(2) the invention realizes the selective recovery of heavy metal ions and avoids the generation of a large amount of dangerous waste residues which are difficult to be recycled;
(3) the tail water solution obtained by the invention is circularly treated, the generated steam condensate water is circularly used, the zero discharge of the waste water and the efficient recovery of resources are realized, and the method has the advantages of low cost, simple operation, cleanness, environmental protection and the like.
Drawings
Fig. 1 is a process flow chart of a stone coal acidic wastewater resource utilization method provided in the section of the embodiment of the invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The specific embodiment of the invention provides a method for recycling stone coal acidic wastewater, and the process flow diagram of the method is shown in figure 1, and the method comprises the following steps:
(1) recovering heavy metal ions in the stone coal acidic wastewater to obtain a heavy metal concentrate and a solution;
(2) enriching the solution obtained in the step (1), adding an iron-containing substance, and carrying out precipitation reaction to obtain jarosite precipitate and a solution;
(3) concentrating and crystallizing the solution obtained in the step (2) to obtain magnesium sulfate solid and solution;
(4) and (3) adding ammonium salt and/or ammonia water into the solution obtained in the step (3), crystallizing to obtain magnesium-nitrogen double salt and a solution, and returning the obtained solution to the step (1).
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, which comprises the following main components in percentage by weight: na (Na)+5.16g/L、K+0.56g/L、NH4 +1.75g/L、Mg2+1.82g/L、SO4 2-8.92g/L, and the stone coal acid wastewater further comprises: vanadium 0.055g/L, chromium 0.0032g/L, nickel 0.0044g/L, copper 0.021g/L, cobalt 0.0039g/L, cadmium 0.0013 g/HL, zinc 0.083g/L, iron 0.086g/L and aluminum 0.023g/L, wherein the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a nitrogen-containing and phosphorus-containing chelate resin adsorbent to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) returning the solution obtained in the step (1) to the stone coal leaching process, and performing multiple circulating leaching and enrichment to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+31.73g/L、K+2.70g/L、Mg2+11.29g/L、NH4 +3.86g/L, adding ferric chloride into the enrichment solution, wherein the addition amount of the ferric chloride is 0.95 times of the theoretical amount required for producing the jarosite, adding hydrochloric acid and sodium hydroxide to adjust and control the pH of the solution so that the pH value of the solution is maintained at about 4 in the reaction process, carrying out precipitation reaction for 0.2h at the temperature of 200 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+0.95g/L、K+0.83g/L、Mg2 +11.18g/L、NH4 +1.69g/L, and recovering iron oxide and sodium sulfate products from the jarosite by a roasting-water washing method;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 0.2h under the conditions that the temperature is 92 ℃ and the vacuum degree is 90kPa, wherein the concentration of each ion in the solution after evaporation is Na+27.41g/L、K+23.96g/L、NH4 +50g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) crystallizing the filtrate obtained in the step (3) at 0 ℃, filtering to obtain magnesium-nitrogen double salt and filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the obtained iron oxide product was 98.67 wt%, the purity of sodium sulfate was 97.48 wt%, the purity of magnesium sulfate was 99.13 wt%, and the purity of magnesium-nitrogen double salt was 97.62 wt% through detection and calculation.
Example 2:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 1, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a natural organic adsorbent to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) returning the solution obtained in the step (1) to the stone coal leaching process, and performing multiple circulating leaching and enrichment to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+150g/L、K+1.14g/L、Mg2+25g/L、NH4 +1.97g/L, adding ferric sulfate into the enrichment solution, wherein the addition amount of ferric sulfate is 0.5 time of the theoretical amount required for producing jarosite, adding sulfuric acid and sodium hydroxide to adjust and control the pH of the solution so that the pH value of the solution is maintained at about-2 in the reaction process, carrying out precipitation reaction for 8 hours at the temperature of 30 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+2.57g/L、K+0.97g/L、Mg2+24.72g/L、NH4 +1.48g/L, washing and deacidifying the jarosite with water, and then directly burying;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 6h at the temperature of 90 ℃ and the vacuum degree of 20kPa, wherein each ion concentration in the solution after evaporation is Na+120.95g/L、K+45.92g/L、NH4 +70g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonium carbonate and ammonium bicarbonate into the filtrate obtained in the step (3), wherein the adding amount of the ammonium carbonate and the ammonium bicarbonate is 2.5 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at 40 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the magnesium sulfate product obtained by detection and calculation is 98.24 wt%, and the purity of the magnesium nitrogen double salt is 96.47 wt%.
Example 3:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 1, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a nitrogen-containing and sulfur-containing chelating resin adsorbent to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) returning the solution obtained in the step (1) to the stone coal leaching process, and performing multiple circulating leaching and enrichment to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+52.51g/L、K+1.56g/L、Mg2+17.32g/L、NH4 +3.67g/L, adding iron-rich minerals and iron-rich tailings into the enrichment solution, wherein the addition amount of the iron-rich minerals and the iron-rich tailings is 3 times of the theoretical amount required for producing the jarosite, adding sulfuric acid and ammonia water to adjust and control the pH of the solution, maintaining the pH value of the solution at about-1 in the reaction process, carrying out precipitation reaction for 6 hours at the temperature of 60 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+0.88g/L、K+0.73g/L、Mg2+16.57g/L、NH4 +1.05g/L, and recovering iron oxide and sodium sulfate products from the jarosite by a roasting-water washing method;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 1.5h under the conditions that the temperature is 70 ℃ and the vacuum degree is 10kPa, wherein the concentration of each ion in the solution after evaporation is Na+19.96g/L、K+17.83g/L、NH4 +25g/L, and filtering to obtain magnesium sulfate crystals and a filtrate;
(4) and (3) adding ammonium sulfate into the filtrate obtained in the step (3), wherein the addition amount of the ammonium sulfate is 1 time of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at the temperature of 20 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, through detection and calculation, the purity of the obtained iron oxide product is 98.98 wt%, the purity of the sodium sulfate is 97.35 wt%, the purity of the magnesium sulfate is 99.38 wt%, and the purity of the magnesium-nitrogen double salt is 96.93 wt%.
Example 4:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 1, and the method comprises the following steps:
(1) reducing hexavalent chromium into trivalent chromium by using low-valent sulfur in the stone coal acidic wastewater, adjusting the pH value of the wastewater to 8, adding sulfide to selectively recover heavy metal to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) evaporating, concentrating and enriching the solution obtained in the step (1) to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+140g/L、K+15.09g/L、Mg2+49.28g/L、NH4 +47.45g/L, adding ferric sulfate into the enriched solution, wherein the addition amount of ferric sulfate is 1.5 times of the theoretical amount required for producing the jarosite, adding sulfuric acid and sodium carbonate to adjust and control the pH of the solution so that the pH value of the solution is maintained at about 3 in the reaction process, carrying out precipitation reaction for 3 hours at the temperature of 101 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+1.83g/L、K+1.63g/L、Mg2+48.97g/L、NH4 +0.89g/L, wherein the jarosite precipitate is a mixture of jarosite, ammonioiarosite and jarosite, ammonia gas and sulfur trioxide generated by roasting the jarosite are recovered to obtain an ammonium sulfate solution, and a roasted material is washed with water to obtain an iron oxide product and an alkali metal sulfate solution;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 1h under the conditions that the temperature is 80 ℃ and the vacuum degree is 80kPa, wherein the concentration of each ion in the solution after evaporation is Na+29.94g/L、K+26.43g/L、NH4 +15g/L, and filtering to obtain magnesium sulfate crystals and a filtrate;
(4) and (3) adding ammonium chloride and ammonium nitrate into the filtrate obtained in the step (3), wherein the addition amount of the ammonium chloride and the ammonium nitrate is 1.5 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at the temperature of 60 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the obtained iron oxide product was 99.04 wt%, the purity of magnesium sulfate was 98.63 wt%, and the purity of the magnesium-nitrogen double salt was 98.78 wt% through detection and calculation.
Example 5:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 1, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a nitrogen-containing chelate resin adsorbent to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) evaporating, concentrating and enriching the solution obtained in the step (1) to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+91.03g/L、K+9.67g/L、Mg2+32.02g/L、NH4 +29.69g/L, adding ferric hydroxide into the enrichment solution, wherein the addition amount is 1 time of the theoretical amount required for producing the jarosite, adding sulfuric acid and sodium hydroxide to adjust and control the pH of the solution, so that the pH value of the solution is maintained at about 2 in the reaction process, carrying out precipitation reaction for 1h at the temperature of 150 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+1.45g/L、K+0.49g/L、Mg2+31.84g/L、NH4 +1.42g/L, the jarosite precipitate is a mixture of jarosite, ammonioiarosite and jarosite, and the jarosite is washed with water and deacidified and then directly buried;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 0.5h at the temperature of 60 ℃ and the vacuum degree of 50kPa, wherein the concentration of each ion in the solution after evaporation is Na+15g/L、K+5.26g/L、NH4 +13.89g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonium sulfate and ammonium bisulfate into the filtrate obtained in the step (3), wherein the adding amount of the ammonium sulfate and the ammonium bisulfate is 1.2 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at the temperature of 10 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the magnesium sulfate product was 98.74 wt% and the purity of the magnesium nitrogen double salt was 98.62 wt% by detection and calculation.
Example 6:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 1, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a phosphorus-containing chelating resin adsorbent to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) evaporating, concentrating and enriching the solution obtained in the step (1) to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+28.39g/L、K+3.09g/L、Mg2+10g/L、NH4 +9.69g/L, adding ferric oxide into the enrichment solution, wherein the addition amount of the ferric oxide is 0.8 time of the theoretical amount required for producing the jarosite, adding sulfuric acid and potassium hydroxide to adjust and control the pH of the solution so that the pH value of the solution is maintained at about 1.3 in the reaction process, carrying out precipitation reaction for 0.5h at 180 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+2.29g/L、K+1.18g/L、Mg2+9.66g/L、NH4 +0.76g/L, wherein the jarosite precipitate is a mixture of jarosite, ammonioiarosite and jarosite, and the jarosite is washed with water to be deacidified and then is directly buried;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 3h at the temperature of 95 ℃ and the vacuum degree of 70kPa, wherein each ion concentration in the solution after evaporation is Na+135g/L、K+69.96g/L、NH4 +46.12g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonia water into the filtrate obtained in the step (3), wherein the addition amount of the ammonia water is 2 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at 80 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the obtained magnesium sulfate product was 98.94 wt%, and the purity of the magnesium nitrogen double salt was 97.86 wt% through detection and calculation.
Example 7:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, which comprises the following main components in percentage by weight: na (Na)+6.52g/L、K+0.73g/L、NH4 +1.92g/L、Mg2+1.69g/L、SO4 2-7.49g/L, and the stone coal acid wastewater also comprises: 0.0084g/L of vanadium, 0.017g/L of chromium, 0.0012g/L of nickel, 0.045g/L of copper, 0.0013g/L of cobalt, 0.0007g/L of cadmium, 0.069g/L of zinc, 0.072g/L of iron and 0.048g/L of aluminum, wherein the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a sulfur-containing chelating resin adsorbent to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) returning the solution obtained in the step (1) to the stone coal leaching process, and performing multiple circulating leaching and enrichment to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+41.79g/L、K+3.47g/L、Mg2+10.36g/L、NH4 +10.67g/L, adding ferric sulfate and ferric hydroxide into the enriched solution, wherein the addition amount of the ferric sulfate and the ferric hydroxide is 0.9 time of the theoretical amount required for producing the jarosite, adding sulfuric acid and sodium hydroxide to adjust and control the pH of the solution, so that the solution is maintained at about 0 in the reaction process, carrying out precipitation reaction for 2 hours at 115 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+1.74g/L、K+1.04g/L、Mg2+10.16g/L、NH4 +1.37g/L, washing and deacidifying the jarosite with water, and then directly burying;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 2 hours at the temperature of 90 ℃ and the vacuum degree of 80kPa, and evaporatingThe concentration of each ion in the post solution is Na+52.05g/L、K+30g/L、NH4 +38.92g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonium sulfate, ammonium bisulfate and ammonium bicarbonate into the filtrate obtained in the step (3), wherein the addition amount of the ammonium sulfate, the ammonium bisulfate and the ammonium bicarbonate is 0.5 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at the temperature of 30 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the obtained magnesium sulfate product was 98.88 wt%, and the purity of the magnesium-nitrogen double salt was 98.25 wt%.
Example 8:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 7, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using an oxygen-containing chelating resin adsorbent to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) returning the solution obtained in the step (1) to the stone coal leaching process, and performing multiple circulating leaching and enrichment to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+78.38g/L、K+8.85g/L、Mg2+18.42g/L、NH4 +15.81g/L, adding ferric sulfate and ferric oxide into the concentrated solution, wherein the addition amount of the ferric sulfate and the ferric oxide is 1.2 times of the theoretical amount required for producing the jarosite, adding sulfuric acid and ammonia water to adjust and control the pH value of the solution, so that the solution is maintained at about 0.5 in the reaction process, carrying out precipitation reaction for 3 hours at the temperature of 120 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+2.69g/L、K+1.62g/L、Mg2+17.28g/L、NH4 +0.85g/L, the jarosite is precipitated to be a mixture of the jarosite, the ammoniojarosite and the jarosite, ammonia gas and sulfur trioxide generated by roasting the jarosite are recovered to obtain an ammonium sulfate solution, and a roasting material is subjected to ammonium sulfate solutionWashing with water to obtain an iron oxide product and an alkali metal sulfate solution;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 4 hours at the temperature of 85 ℃ and the vacuum degree of 50kPa, wherein each ion concentration in the solution after evaporation is Na+90g/L、K+54.79g/L、NH4 +27.45g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonium bisulfate and ammonia water into the filtrate obtained in the step (3), wherein the addition amount of the ammonium bisulfate and the ammonia water is 0.8 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at 40 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the obtained iron oxide product was 98.35 wt%, the purity of magnesium sulfate was 99.37 wt%, and the purity of the magnesium-nitrogen double salt was 97.94 wt% through detection and calculation.
Example 9:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 7, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a chelate resin adsorbent containing nitrogen, phosphorus, oxygen and sulfur to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) evaporating, concentrating and enriching the solution obtained in the step (1) to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+115.05g/L、K+12.89g/L、Mg2+30g/L、NH4 +33.94g/L, adding iron oxide into the enrichment solution, wherein the addition amount of the iron oxide is 0.1 time of the theoretical amount required for producing the jarosite, adding sulfuric acid and potassium hydroxide to adjust and control the pH of the solution so that the pH value of the solution is maintained at about 1 in the reaction process, carrying out precipitation reaction for 4 hours at the temperature of 80 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+1.28g/L、K+0.69g/L、Mg2+28.89g/L、NH4 +0.73g/L, precipitating the jarosite to be a mixture of the jarosite, the ammonioiarosite and the jarosite, recovering ammonia gas and sulfur trioxide generated by roasting the jarosite to obtain an ammonium sulfate solution, and washing the roasted material with water to obtain an iron oxide product and an alkali metal sulfate solution;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 3.5h at the temperature of 90 ℃ and the vacuum degree of 60kPa, wherein the concentration of each ion in the solution after evaporation is Na+84.64g/L、K+45g/L、NH4 +46.92g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonium sulfate into the filtrate obtained in the step (3), wherein the adding amount of the ammonium sulfate is 1.8 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at 50 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circulating treatment.
In this example, the purity of the obtained iron oxide product was 99.27 wt%, the purity of magnesium sulfate was 98.59 wt%, and the purity of the magnesium-nitrogen double salt was 97.38 wt% through detection and calculation.
Example 10:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 7, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a chelate resin adsorbent containing nitrogen, phosphorus and oxygen to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) evaporating, concentrating and enriching the solution obtained in the step (1) to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+123.48g/L、K+12.89g/L、Mg2+32.45g/L、NH4 +36.82g/L, adding iron hydroxide and iron oxide into the enrichment solution, wherein the addition amount is 0.3 time of the theoretical amount required for producing jarosite, adding sulfuric acid and sodium hydroxide to adjust and control the pH value of the solution, and enabling the solution to react in the reaction processMaintaining the concentration of Na in the filtrate at about 1.2, precipitating at 160 deg.C for 0.8 hr, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+3.77g/L、K+3.37g/L、Mg2+32.04g/L、NH4 +1.80g/L, the jarosite precipitate is a mixture of jarosite, ammonioiarosite and jarosite, and is subjected to washing deacidification and direct landfill treatment;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 0.8h under the conditions that the temperature is 100 ℃ and the vacuum degree is 80kPa, wherein the concentration of each ion in the solution after evaporation is Na+88.95g/L、K+80g/L、NH4 +43.29g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonium sulfate into the filtrate obtained in the step (3), wherein the adding amount of the ammonium sulfate is 0.9 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at the temperature of 80 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the magnesium sulfate product was 98.84 wt% and the purity of the magnesium-nitrogen double salt was 98.75 wt% by detection and calculation.
Example 11:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 7, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a microbial adsorbent to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) evaporating, concentrating and enriching the solution obtained in the step (1) to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+58.32g/L、K+6.67g/L、Mg2+15.38g/L、NH4 +17.49g/L, adding ferric sulfate into the enriched solution, wherein the addition amount of the ferric sulfate is 2 times of the theoretical amount required for producing the jarosite, adding sulfuric acid and ammonia water to adjust and control the pH value of the solution so as to enable the solution to reactMaintaining at about 0.3 deg.C, precipitating at 140 deg.C for 1.5h, filtering to obtain jarosite precipitate and filtrate, wherein each ion concentration in the filtrate is Na+2.58g/L、K+0.84g/L、Mg2+14.19g/L、NH4 +1.92g/L, the jarosite precipitate is a mixture of jarosite, ammonioiarosite and jarosite, and is subjected to washing deacidification and direct landfill treatment;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 1h at the temperature of 85 ℃ and the vacuum degree of 90kPa, wherein each ion concentration in the solution after evaporation is Na+30g/L、K+9.84g/L、NH4 +22.82g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonium bisulfate into the filtrate obtained in the step (3), wherein the addition amount of the ammonium bisulfate is 0.2 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at the temperature of 25 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circulating treatment.
In this example, the purity of the obtained magnesium sulfate product was 97.95 wt%, and the purity of the magnesium-nitrogen double salt was 98.83 wt%.
Example 12:
the embodiment provides a method for resource utilization of stone coal acidic wastewater, wherein the components and the concentration in the stone coal acidic wastewater refer to embodiment 7, and the method comprises the following steps:
(1) selectively recovering heavy metals from the stone coal acidic wastewater by using a chelate resin adsorbent containing nitrogen, phosphorus and sulfur to obtain a heavy metal concentrate and a solution, wherein the concentrations of vanadium, chromium, nickel, copper, cobalt, cadmium, zinc, iron and aluminum in the solution are all less than 0.1ppm, and the heavy metal concentrate is separated and recovered according to the prior art;
(2) returning the solution obtained in the step (1) to the stone coal leaching process, and performing multiple circulating leaching and enrichment to obtain a high-concentration salt-containing solution, wherein each ion concentration in the high-concentration salt-containing solution is Na+45.16g/L、K+0.94g/L、Mg2+10.74g/L、NH4 +0.54g/L, adding ferric sulfate into the enriched liquid, wherein the addition amount of the ferric sulfate is 2.5 times of the theoretical amount required for producing jarositeAdding sulfuric acid and sodium hydroxide to adjust and control the pH value of the solution to be maintained at about 0.8 in the reaction process, carrying out precipitation reaction for 2 hours at 105 ℃, and filtering to obtain jarosite precipitate and filtrate, wherein the concentration of each ion in the filtrate is Na+1.63g/L、K+0.71g/L、Mg2 +10.74g/L、NH4 +0.54g/L, and recovering iron oxide and sodium sulfate products from the jarosite by a roasting-washing method;
(3) evaporating and crystallizing the filtrate obtained in the step (2) for 5 hours at the temperature of 75 ℃ and the vacuum degree of 70kPa, wherein each ion concentration in the solution after evaporation is Na+125.77g/L、K+55g/L、NH4 +41.73g/L, and filtering to obtain magnesium sulfate crystals and filtrate;
(4) and (3) adding ammonium bisulfate and ammonium bicarbonate into the filtrate obtained in the step (3), wherein the addition amount of the ammonium bisulfate and the ammonium bicarbonate is 0.7 times of the theoretical amount required for generating the magnesium-nitrogen double salt, crystallizing at 35 ℃, filtering to obtain the magnesium-nitrogen double salt and the filtrate, and returning the filtrate to the step (1) for circular treatment.
In this example, the purity of the obtained iron oxide product was 99.35 wt%, the purity of magnesium sulfate was 99.21 wt%, and the purity of the magnesium-nitrogen double salt was 98.63 wt% through detection and calculation.
By combining the embodiments, the stone coal acidic wastewater is separated and recovered with heavy metal ions, and then the jarosite, the magnesium sulfate and the magnesium-nitrogen double salt are respectively obtained by a multi-step crystallization method, so that the high-efficiency separation and recovery of different components in the wastewater are realized, various products with high added values are obtained, the product purity is high, no heavy metal is entrained, the wastewater is returned to the process after being treated for recycling, the zero discharge of the wastewater is realized, and the method has the advantages of low cost, simplicity in operation, cleanness, environmental protection and the like.
The applicant states that the process of the present invention is illustrated by the above examples, but the present invention is not limited to the above process, i.e. it is not meant that the present invention must rely on the above process to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (76)
1. A method for resource utilization of stone coal acidic wastewater is characterized by comprising the following steps:
(1) recovering heavy metal ions in the stone coal acidic wastewater, wherein the heavy metal ions are recovered by adopting an adsorption method or a precipitation method, a precipitator used in the precipitation method is a sulfide, and a heavy metal enrichment and a solution are obtained, wherein the heavy metal enrichment comprises a combination of at least two of vanadium, chromium, iron, cobalt, nickel, copper, zinc or cadmium;
(2) enriching the solution obtained in the step (1) to obtain a high-concentration salt-containing solution containing Mg2+、Na+、K+And NH4 +The enrichment method comprises the steps of returning to a stone coal leaching process for cyclic leaching or evaporative concentration, adding an iron-containing substance, wherein the addition amount of the iron-containing substance is 0.1-3 times of the theoretical amount required for producing the jarosite, carrying out a precipitation reaction, wherein the pH value of the precipitation reaction is-2-4, the temperature of the precipitation reaction is 30-200 ℃, and obtaining jarosite precipitate and a solution;
(3) concentrating and crystallizing the solution obtained in the step (2) to obtain magnesium sulfate solid and solution;
(4) adding ammonium salt and/or ammonia water into the solution obtained in the step (3), and crystallizing to obtain magnesium-nitrogen double salt MgSO4·(NH4)2SO4·6H2O and the solution, and returning the obtained solution to the step (1).
2. The method according to claim 1, wherein the stone coal acidic wastewater in the step (1) is stone coal sulfuric acid process vanadium extraction process wastewater.
3. The method according to claim 1, wherein the stone coal acidic wastewater in the step (1) does not contain Cl－And F－。
4. The method as claimed in claim 1, wherein the pH of the stone coal acidic wastewater in the step (1) is less than 7.
5. The method according to claim 4, wherein the pH of the stone coal acidic wastewater in the step (1) is 0-6.
6. The method of claim 1, wherein the heavy metal ion recovery in step (1) is performed by adsorption.
7. The method according to claim 1, wherein the adsorbent used in the adsorption method is a chelating resin and/or a biosorbent.
8. The method of claim 7, wherein the functional group of the chelating resin comprises any one of a nitrogen-containing functional group, a phosphorus-containing functional group, an oxygen-containing functional group, or a sulfur-containing functional group, or a combination of at least two thereof.
9. The method according to claim 8, wherein the functional group of the chelating resin is a nitrogen-containing functional group and/or a phosphorus-containing functional group.
10. The method of claim 7, wherein the biological adsorbent comprises any one or a combination of at least two of natural organic adsorbents and modifications thereof, microorganisms and modifications thereof, or agricultural, forestry, animal husbandry and fishery waste and modifications thereof.
11. The method of claim 1, wherein the sulfide comprises any one of sodium sulfide, potassium sulfide, ammonium sulfide, sodium hydrosulfide, potassium hydrosulfide, or ammonium hydrosulfide, or a combination of at least two thereof.
12. The method of claim 1, wherein the concentrate of step (1) further comprises aluminum and arsenic.
13. The method according to claim 1, wherein the enrichment method in the step (2) is a recycling leaching of the stone coal leaching process.
14. The method according to claim 1, wherein the enrichment method in the step (2) is to return to stone coal leaching for cyclic leaching, and the high-concentration salt solution contains Mg2+The concentration is 10-25 g/L.
15. The method of claim 14, wherein the high concentration salt-containing solution contains Mg2+The concentration is 15-20 g/L.
16. The method according to claim 1, wherein the enrichment method in the step (2) is to return to the stone coal leaching process for cyclic leaching, and Na in the high-concentration salt-containing solution+The concentration is less than or equal to 150 g/L.
17. The method of claim 16, wherein the high concentration salt-containing solution contains Na+The concentration is less than or equal to 130 g/L.
18. The method of claim 17, wherein the high concentration salt-containing solution contains Na+The concentration is less than or equal to 90 g/L.
19. The method according to claim 1, wherein the enrichment method in the step (2) is to return to stone coal leaching for cyclic leaching, and K in the high-concentration salt-containing solution+The concentration is less than or equal to 70 g/L.
20. The method of claim 19, wherein K is in the high concentration salt-containing solution+The concentration is less than or equal to 60 g/L.
21. The method of claim 20, wherein K in the high concentration salt-containing solution+The concentration is less than or equal to 55 g/L.
22. The method according to claim 1, wherein the enrichment method in step (2) is to return NH in the high-concentration salt-containing solution to stone coal leaching process for cyclic leaching4 +The concentration is less than or equal to 40 g/L.
23. The method of claim 22, wherein the high concentration salt-containing solution comprises NH4 +The concentration is less than or equal to 30 g/L.
24. The method according to claim 1, wherein when the enrichment method in the step (2) is evaporation concentration, Mg in the high-concentration salt-containing solution2+The concentration is 10-60 g/L.
25. The method of claim 24, wherein the high concentration salt-containing solution contains Mg2+The concentration is 20-60 g/L.
26. The method of claim 25, wherein the high concentration salt-containing solution contains Mg2+The concentration is 30-60 g/L.
27. The method according to claim 1, wherein in the case that the enrichment method in the step (2) is evaporative concentration, Na in the high-concentration salt-containing solution+The concentration is less than or equal to 155 g/L.
28. The method of claim 27, wherein the high concentration salt-containing solution contains Na+The concentration is less than or equal to 140 g/L.
29. The method according to claim 1, wherein when the enrichment method in the step (2) is evaporation concentration, K is contained in the high-concentration salt-containing solution+The concentration is less than or equal to 105 g/L.
30. The method of claim 29, wherein K is in the high concentration salt-containing solution+The concentration is less than or equal to 95 g/L.
31. The method according to claim 1, wherein, when the enrichment method in the step (2) is evaporation concentration, NH in the high-concentration salt-containing solution4 +The concentration is less than or equal to 90 g/L.
32. The method of claim 31, wherein the high-concentration salt-containing solution contains NH4 +The concentration is less than or equal to 70 g/L.
33. The method of claim 1, wherein the iron-containing substance of step (2) comprises any one of iron sulfate, iron chloride, iron nitrate, iron phosphate, iron hydroxide, iron oxide, iron-rich minerals, or iron-rich tailings, or a combination of at least two thereof.
34. The method of claim 33, wherein the iron-containing substance of step (2) is any one of iron sulfate, iron hydroxide or iron oxide or a combination of at least two of the foregoing.
35. The method of claim 34, wherein the iron-containing species of step (2) is iron sulfate.
36. The method according to claim 1, wherein the iron-containing material is added in an amount of 0.5 to 1.5 times the theoretical amount required to produce jarosite.
37. The method of claim 36, wherein the iron-containing material is added in an amount of 0.8 to 1 times the theoretical amount required to produce jarosite.
38. The method according to claim 1, wherein the composition of the jarosite is MFe3(SO4)2(OH)6Wherein M is Na+、NH4 +Or K+Any one or at least two ofA combination of species.
39. The method according to claim 1, wherein the precipitation reaction in step (2) has a pH of-1 to 3.
40. The method according to claim 39, wherein the precipitation reaction in step (2) has a pH of 0 to 1.3.
41. The method of claim 39, wherein the pH is adjusted with an acidic or basic substance.
42. The method of claim 41, wherein the acidic substance comprises any one of hydrochloric acid, nitric acid, phosphoric acid, or sulfuric acid, or a combination of at least two thereof.
43. The method of claim 42, wherein the acidic material is sulfuric acid.
44. The method of claim 41, wherein the alkaline substance comprises any one of sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate, or a combination of at least two thereof.
45. The method of claim 44, wherein the alkaline substance is any one of sodium hydroxide, potassium hydroxide or ammonia water or a combination of at least two of the above.
46. The method according to claim 1, wherein the precipitation reaction in step (2) is carried out at a temperature of 60 to 150 ℃.
47. The method according to claim 46, wherein the precipitation reaction in step (2) is carried out at a temperature of 101-150 ℃.
48. The method according to claim 1, wherein the precipitation reaction time in the step (2) is 0.2-8 h.
49. The method as claimed in claim 48, wherein the precipitation reaction time in step (2) is 0.5-6 h.
50. The method as claimed in claim 49, wherein the precipitation reaction time in step (2) is 1-4 h.
51. The method of claim 1, wherein the jarosite precipitate of step (2) is used for recovery of valuable components or for landfill disposal.
52. The process of claim 51, wherein said jarosite precipitate is recovered as an ammonium sulfate solution, ferric oxide and an alkali metal sulfate solution.
53. The method as claimed in claim 52, wherein the ammonium sulfate is used in the process of vanadium extraction from stone coal and/or returned to the step (4) for preparing magnesium nitrogen double salt.
54. The method of claim 52, wherein the iron oxide is returned to step (2) as an iron-containing material.
55. The method of claim 1, wherein the concentrating of step (3) is an evaporation process.
56. The method according to claim 55, wherein the evaporation treatment is reduced pressure evaporation, and the degree of vacuum of the reduced pressure evaporation is 10-90 kPa.
57. The method as claimed in claim 55, wherein the evaporation temperature is 60-100 ℃.
58. The method as claimed in claim 55, wherein the evaporation treatment time is 0.2-6 h.
59. The method as recited in claim 55, wherein said evaporating NH from said solution4 +The concentration is less than or equal to 70 g/L.
60. The method as claimed in claim 59, wherein the NH in the solution after the evaporation treatment4 +The concentration is less than or equal to 50 g/L.
61. The method of claim 55, wherein the evaporation treated solution contains Na+The concentration is less than or equal to 135 g/L.
62. The method of claim 61, wherein the evaporation treated solution contains Na+The concentration is less than or equal to 90 g/L.
63. The method of claim 55, wherein K is in the solution after the evaporation treatment+The concentration is less than or equal to 80 g/L.
64. The method of claim 63, wherein K is in the solution after the evaporation treatment+The concentration is less than or equal to 50 g/L.
65. The method as claimed in claim 55, wherein the steam obtained from the evaporation treatment is condensed and used in the process of extracting vanadium from stone coal.
66. The method of claim 1, wherein the ammonium salt of step (4) comprises any one of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium bisulfate, ammonium carbonate or ammonium bicarbonate or a combination of at least two thereof.
67. The method according to claim 66, wherein the ammonium salt in step (4) is any one of ammonium sulfate, ammonium bisulfate, ammonium carbonate or ammonium bicarbonate or a combination of at least two thereof.
68. The method according to claim 67, wherein the ammonium salt of step (4) is ammonium sulfate and/or ammonium bisulfate.
69. The method of claim 1, wherein the ammonium salt and/or the aqueous ammonia of step (4) is added in an amount to produce magnesium-nitrogen double salt MgSO4·(NH4)2SO4·6H2O is 0 to 2.5 times of the theoretical amount required.
70. The method as claimed in claim 69, wherein the ammonium salt and/or the ammonia water of step (4) is added in an amount of MgSO (MgSO) for producing the magnesium-nitrogen double salt4·(NH4)2SO4·6H2O is 0.2 to 1.2 times of the theoretical amount required.
71. The method according to claim 1, wherein the temperature of the crystallization in the step (4) is 0 to 100 ℃.
72. The method as claimed in claim 71, wherein the temperature of the crystallization in the step (4) is 10-60 ℃.
73. The method as claimed in claim 72, wherein the temperature of the crystallization in the step (4) is 20-40 ℃.
74. The method according to claim 1, wherein the magnesium-nitrogen double salt of step (4) is used as a magnesium-nitrogen compound fertilizer.
75. The method as claimed in claim 1, wherein the magnesium nitrogen double salt of step (4) is used in agricultural production and/or forestry production.
76. The method according to any one of claims 1-75, characterized in that the method comprises the steps of:
(1) recovering heavy metal ions in the stone coal acidic wastewater by adopting an adsorption method or a precipitation method, wherein a precipitator used in the precipitation method is sulfide to obtain a heavy metal enrichment and a solution, and the heavy metal enrichment comprises a combination of at least two of vanadium, chromium, iron, cobalt, nickel, copper, zinc or cadmium;
(2) returning the solution obtained in the step (1) to the stone coal leaching process for cyclic leaching or evaporation concentration enrichment to obtain a high-concentration salt-containing solution containing Mg2+、Na+、K+And NH4 +Adding an iron-containing substance, wherein the addition amount of the iron-containing substance is 0.1-3 times of the theoretical amount required for producing the jarosite, adjusting the pH value of the solution to-2-4, and carrying out precipitation reaction at 30-200 ℃ for 0.2-8 h to obtain jarosite precipitate and a solution;
(3) evaporating and crystallizing the solution obtained in the step (2), wherein the evaporation treatment vacuum degree is 10-90 kPa, the temperature is 60-100 ℃, and the time is 0.2-6 h, so as to obtain magnesium sulfate solid and solution;
(4) and (3) adding ammonium salt and/or ammonia water into the solution obtained in the step (3), crystallizing at the temperature of 0-100 ℃, separating to obtain magnesium-nitrogen double salt and the solution, and returning the obtained solution to the step (1) for circular treatment.
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