CN110171885B - 锂离子电池材料生产中废气废水的回收处理方法 - Google Patents
锂离子电池材料生产中废气废水的回收处理方法 Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000002912 waste gas Substances 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 238000005188 flotation Methods 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 7
- 238000007667 floating Methods 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 4
- -1 hydroxyl ions Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- 239000010842 industrial wastewater Substances 0.000 claims description 3
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 239000002894 chemical waste Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract 1
- 239000003570 air Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- MSMNVXKYCPHLLN-UHFFFAOYSA-N azane;oxalic acid;hydrate Chemical compound N.N.O.OC(=O)C(O)=O MSMNVXKYCPHLLN-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- DDXROPFGVVLFNZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) tricarbonate Chemical compound [Mn+2].[Co+2].C([O-])([O-])=O.[Ni+2].C([O-])([O-])=O.C([O-])([O-])=O DDXROPFGVVLFNZ-UHFFFAOYSA-H 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/28—Ammonium phosphates
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- C—CHEMISTRY; METALLURGY
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- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/18—Nitrates of ammonium
- C01C1/185—Preparation
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- C02F1/24—Treatment of water, waste water, or sewage by flotation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
本发明公开了一种锂离子电池材料生产中废气废水的回收处理方法，属于化工废气废水回收处理技术领域。所述处理方法包括：(1)将锂离子电池材料生产过程中产生的废气和/或废水通入反应釜的水中，通过化学反应生成沉淀物；(2)利用气泵将气体从反应釜底端通入水体中，产生的气泡将水体中的悬浮杂质浮至水体液面；(3)将水体液面上的杂质浮选物捞出，再对反应釜中的水体进行固液分离；(4)分离得到的固体进行干燥，得到副产物；固液分离后剩余的水重新用于废气废水的回收处理。本发明通过引入化学反应与气浮选联用技术实现了锂电材料产业全方位高效利用与分级提纯，实现产业用原材料高效利用，获得锂电材料主产品的同时，又得到工业副产品。
Description
技术领域
本发明涉及化工废气废水回收处理技术领域，具体涉及锂离子电池材料生产中产生的废气废水的回收处理方法。
背景技术
锂离子电池因其能量高、放电时间长、体积小、环境适用性强、无记忆性等特点而得以迅速发展，相应的磷酸铁锂、三元材料、钴酸锂、磷酸锰铁锂等材料以及它们的前躯体产业材料也迅速发展。但是工业生产中排放大量未经处理的水、气、渣等有害废物，会严重地破坏农业的生态平衡和自然资源，对农业生产的发展造成极大的危害。
目前产业化锂电材料的制备主要采用固相合成法，所用的原材料主要以碳酸锂、氢氧化锂等为锂源，草酸亚铁、乙二酸亚铁、磷酸二氢铵、氢氧化镍钴锰、镍钴锰碳酸盐、磷酸铁、磷酸锰铁等为活性物质原材料，以磷酸二氢铵、硝酸铝、蔗糖、葡萄糖等作为材料改性原材料；同时，目前制备锂电材料所用的活性物质原材料大部分是通过湿法反应制备，如磷酸铁通过铁与磷酸反应制备，氢氧化镍钴锰通过镍、钴、锰的硫酸盐或氯化物与氢氧化钠、氨水等反应制备。在材料制备过程中产生的大量氨气、氮氧化物、二氧化碳及有机悬浮物。
但目前锂电材料在其制备过程中，仅仅专注于锂电材料的制备，不但没有充分利用好原材料，而且存在将废气废水用水稀释后直接排掉的现象，造成严重的环境污染。因此，急需一种有效的方法对锂电材料制备过程中产生的废气废水进行处理，以减轻对环境的污染。
发明内容
针对现有技术不足，本发明的目的是提供一种锂电材料产业全方位高效利用与分级提纯方法，解决锂离子电池材料制备过程中存在的原材料浪费与环境污染严重的问题。
为实现上述目的，本发明采用如下技术方案：
锂离子电池材料生产中废气废水的回收处理方法，包括以下步骤：
(1)将锂离子电池材料生产过程中产生的废气和/或废水通入反应釜的水中，通过化学反应生成沉淀物；
(2)利用气泵将气体从反应釜底端通入水体中，产生的气泡将水体中的悬浮杂质浮至水体液面；
(3)将水体液面上的杂质浮选物捞出，再对反应釜中的水体进行固液分离；
(4)分离得到的固体进行干燥，得到副产物；固液分离后剩余的水重新用于废气废水的回收处理。
所述的锂离子电池材料可为磷酸铁锂、磷酸锰铁锂、掺杂包覆型三元材料、掺杂包覆型钴酸锂、石墨材料、硅碳材料等锂电材料中的任意一种或磷酸铁、磷酸锰铁、氢氧化镍钴锰、镍钴锰碳酸盐、碳酸锰、氢氧化钴等锂电前躯体材料中的任意一种。所述的废气或废水即为在上述材料制备过程中产生的。
步骤(1)中，所述的废气为氨气、二氧化碳、二氧化硫、二氧化氮中的任意一种或多种；
所述的废水为硫酸、盐酸、磷酸、草酸中的任意一种或多种。
具体地，例如当通入水中的废气中同时含有氨气、二氧化碳时，即会发生化学反应生成碳酸氢铵或碳酸铵沉淀，化学反应式为：NH3+CO2+H2O→NH4HCO3↓。
步骤(1)中，往含有废气废水的水体中添加添加剂，所述添加剂为氢氧化钡、氯化钡、氯化钙、氯化铁中的任意一种或多种，或者为硫酸、盐酸、磷酸、草酸中的任意一种或多种。不同的废气废水类型与相应的添加剂按照化学计量比发生反应，如：NaSO4+BaCl2→BaSO4↓+2NaCl。
步骤(2)中，气体从反应釜底端两侧通入，通过气泡顶托、气泡裹携和气粒吸附作用将废水中有机分子浮到水面。
所述气体为空气、氧气或二氧化碳气体。
优选的，步骤(2)中，所述气体通入水体的流速为0.1-10m3/h。
优选的，步骤(2)中，通气体浮选的时间为2-10h。具体时间根据废水废气的处理量进行调整。
步骤(3)中，固液分离的方法为过滤、离心、压滤中的任意一种或多种。
步骤(4)中，由于废气或废水中的组分复杂，经固液分离后剩余的水中可能还含有其他化学物质，再重复上述步骤(1)-(4)进行沉淀、分离，分步对各组分进行去除，同时获得相应的工业副产品。
所述干燥为烘干、微波干燥或风干。
本发明具备的有益效果：
本发明通过引入化学反应与气浮选联用技术突破了锂电材料产业全方位高效利用与分级提纯技术难题，实现产业用原材料100％高效利用，获得锂电材料主产品的同时，又得到高纯度碳酸氢铵、碳酸铵、硝酸铵或磷酸铵等工业副产品。
实现了产业废水废气的零排放与净化废水的循环利用，实现“零废气零废水”排放，处理成本大幅降低。
附图说明
图1为本发明所用的工艺流程示意图。
图2为本发明实施例1回收利用所制备水合草酸铵的扫描电镜图。
图3为本发明实施例1回收利用所制备水合草酸铵的XRD图。
具体实施方式
下面通过部分实施例详细描述本发明的制备工艺，但这并非是对本发明的限制，本领域技术人员根据本发明的基本思想，可以做出各种修改或改进，只要不脱离本发明的基本思想，均在本发明的保护范围之内。
对比例1
将磷酸铁锂材料制备过程中产生的含有氨气、二氧化碳与有机分子的废气通入70L水中，得到四组氨含量和有色悬浮物的废水样品；以0.1MNa2CO3水溶液标定好的盐酸溶液为滴定剂，以甲基红溶液为指示剂，对吸收废气后的不同废水进行氨含量的测定，发现所排出的废水中铵含量很高，其结果如表1所示。
表1不同废水样品的氨含量测试结果
| 废水样品 | 1# | 2# | 3# | 4# |
| 氨含量/M | 1.82M | 3.2M | 2.6M | 1.2M |
实施例1
将磷酸铁锂材料制备过程中产生的含有氨气、二氧化碳、有机分子等组分的废气通入反应釜中，以0.1M Na2CO3水溶液标定好的盐酸溶液为滴定剂，以甲基红溶液为指示剂，对吸收废气后的1#废水进行氨含量的测定，测得氨含量为1.82M；利用气泵将空气从反应釜底端两侧通入反应釜中，通过气泡顶托、气泡裹携和气粒吸附作用将废水中有机分子浮到水面；同时将78.4g H2C2O4·2H2O缓慢加入到反应釜中，待反应完毕后继续通空气浮选2小时，将水面上的悬浮物捞出，然后将沉淀物从反应釜侧下角取出，洗涤并加热干燥后得到产物纯度较高的草酸铵副产品(其杂质量如表2所示)，表面形貌和结构分别如图2和图3所示；所得到分级净化后的水用于产业废气的循环回收利用；整体处理流程如图1所示。
表2 1#废水净化回收所得沉淀物的ICP测试结果
实施例2
将磷酸锰铁锂材料制备过程中产生的含有氨气、二氧化碳、有机分子等组分的废气同时通入反应釜中，氨气与二氧化碳发生化学反应并生成碳酸氢铵或碳酸铵沉淀，同时利用气泵将空气从反应釜底端两侧通入反应釜中，通过气泡顶托、气泡裹携和气粒吸附作用将废水中有机分子浮到水面；待反应完毕后继续通空气浮选3小时，将水面上的悬浮物捞出，然后将沉淀物从反应釜侧下角取出，洗涤并加热干燥后得到纯度较高的碳酸铵或碳酸氢铵副产品，所得到分级净化后的水用于产业废气的循环回收利用。
实施例3
将氢氧化镍钴锰材料制备过程中产生的含有硫酸根离子、氢氧根离子、铵根离子、钠离子的废水通入反应釜中，然后往里添加氢氧化钡，待反应完毕后将沉淀物从反应釜侧下角取出，洗涤干燥后所得纯度较高的硫酸钡副产品；然后将镍钴锰酸锂材料烧结制备过程中产生的含有二氧化碳与有机分子的废气通入到反应釜中，同时利用气泵将空气从反应釜底端两侧通入反应釜中，通过气泡顶托、气泡裹携和气粒吸附作用将废水中有机分子浮到水面；待反应完毕后继续通空气浮选3小时，将水面上的悬浮物捞出，然后将沉淀物从反应釜侧下角取出，洗涤并加热干燥后得到纯度较高的碳酸铵副产品，所得到分级净化后的水用于产业废水的循环回收利用。
Claims (1)
1.锂离子电池材料生产中废气废水的回收处理方法，其特征在于，包括以下步骤：
将磷酸铁锂材料制备过程中产生的含有氨气、二氧化碳、有机分子组分的废气通入反应釜中，以0.1M Na2CO3水溶液标定好的盐酸溶液为滴定剂，以甲基红溶液为指示剂，对吸收废气后的废水进行氨含量的测定，测得氨含量为1.82 M；利用气泵将空气从反应釜底端两侧通入反应釜中，通过气泡顶托、气泡裹携和气粒吸附作用将废水中有机分子浮到水面；同时将78.4g H2C2O4·2H2O加入到反应釜中，待反应完毕后继续通空气浮选2小时，将水面上的悬浮物捞出，然后将沉淀物从反应釜侧下角取出，洗涤并加热干燥后得到草酸铵副产品；所得到分级净化后的水用于产业废气的循环回收利用；
或者，将氢氧化镍钴锰材料制备过程中产生的含有硫酸根离子、氢氧根离子、铵根离子、钠离子的废水通入反应釜中，然后往里添加氢氧化钡，待反应完毕后将沉淀物从反应釜侧下角取出，洗涤干燥后所得硫酸钡副产品；然后将镍钴锰酸锂材料烧结制备过程中产生的含有二氧化碳与有机分子的废气通入到反应釜中，同时利用气泵将空气从反应釜底端两侧通入反应釜中，通过气泡顶托、气泡裹携和气粒吸附作用将废水中有机分子浮到水面；待反应完毕后继续通空气浮选3小时，将水面上的悬浮物捞出，然后将沉淀物从反应釜侧下角取出，洗涤并加热干燥后得到碳酸铵副产品，所得到分级净化后的水用于产业废水的循环回收利用。
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