CN117085638A - Efficient defluorination medicament suitable for lithium battery wastewater and application thereof - Google Patents
Efficient defluorination medicament suitable for lithium battery wastewater and application thereof Download PDFInfo
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- CN117085638A CN117085638A CN202311181699.1A CN202311181699A CN117085638A CN 117085638 A CN117085638 A CN 117085638A CN 202311181699 A CN202311181699 A CN 202311181699A CN 117085638 A CN117085638 A CN 117085638A
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- Prior art keywords
- wastewater
- cyclodextrin
- high efficiency
- hydroxyapatite
- agent according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002351 wastewater Substances 0.000 title claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 41
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 20
- 239000003814 drug Substances 0.000 title claims abstract description 19
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 22
- 244000005700 microbiome Species 0.000 claims abstract description 22
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 20
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 18
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 9
- 241000894006 Bacteria Species 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- -1 carboxyethyl Chemical group 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000013177 MIL-101 Substances 0.000 claims description 6
- 239000013206 MIL-53 Substances 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000001116 FEMA 4028 Substances 0.000 claims description 4
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 4
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 4
- 229960004853 betadex Drugs 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003344 environmental pollutant Substances 0.000 abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 10
- 231100000719 pollutant Toxicity 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 abstract description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 150000002500 ions Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CUJVBAPGYBSBHJ-YWBSARSQSA-N 2-[[(1R,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21R,23R,25R,26R,28R,30R,31R,33R,35R,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-36,38,40,42-tetrakis(carboxymethoxy)-10,15-bis(carboxymethoxymethyl)-37,39,41,43,44,45,46,47,48,49-decahydroxy-20,25,30,35-tetrakis(hydroxymethyl)-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontan-5-yl]methoxy]acetic acid Chemical compound OC[C@H]1O[C@@H]2O[C@H]3[C@H](O)[C@@H](O)[C@H](O[C@@H]3COCC(O)=O)O[C@H]3[C@H](O)[C@@H](O)[C@H](O[C@@H]3COCC(O)=O)O[C@H]3[C@H](O)[C@@H](O)[C@H](O[C@@H]3COCC(O)=O)O[C@@H]3[C@@H](CO)O[C@H](O[C@@H]4[C@@H](CO)O[C@H](O[C@@H]5[C@@H](CO)O[C@H](O[C@H]1[C@H](OCC(O)=O)[C@H]2O)[C@H](O)[C@H]5OCC(O)=O)[C@H](O)[C@H]4OCC(O)=O)[C@H](O)[C@H]3OCC(O)=O CUJVBAPGYBSBHJ-YWBSARSQSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 241000863430 Shewanella Species 0.000 description 2
- 241000625311 Shewanella piezotolerans Species 0.000 description 2
- 241000285040 Shewanella piezotolerans WP3 Species 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 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
- 239000002131 composite material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000018109 developmental process 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
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003960 organic solvent Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/346—Iron bacteria
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The present invention relates to a kind ofThe efficient defluorination medicament is suitable for lithium electric wastewater and application thereof. The efficient defluorination medicament comprises hydroxyapatite, polyaluminum chloride and H 2 O 2 The filler is a porous material with a cyclodextrin derivative loaded on the surface, the cyclodextrin derivative comprises carboxylated cyclodextrin, the porous material is MOFs containing aluminum, and the redox microorganism comprises iron reducing bacteria. The defluorination medicament provided by the invention has the advantages that the raw materials are matched cooperatively, so that the defluorination medicament can remove fluorine efficiently and rapidly, and can treat various pollutants such as organic matters, phosphates, heavy metals and the like in lithium electric wastewater, and the raw materials are economical and environment-friendly, so that the defluorination medicament has a good application prospect.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a high-efficiency defluorination medicament suitable for lithium battery wastewater and application thereof.
Background
Lithium batteries are widely used in the fields of electronic devices, electric vehicles, energy storage systems, and the like, because of their high energy density and long life. With the advancement of clean energy and electric power, the lithium battery industry is rapidly rising and has been developed to a great extent. In the production process of lithium batteries, particularly in the preparation of lithium compounds and the preparation of electrolytes, a large amount of wastewater containing fluoride ions is generated.
Fluoride ions in lithium battery wastewater are a toxic and corrosive substance, and pose potential risks to the environment and human health. Therefore, the method has important significance for reasonable treatment and recovery of fluorine-containing substances in the lithium battery wastewater, not only can reduce environmental pollution, but also can realize recycling of resources. Current common technologies for treating fluorine-containing wastewater of lithium batteries include physical and chemical methods (such as precipitation, adsorption and ion exchange) and biological methods. However, these techniques have drawbacks such as the large amount of reagents and equipment required for the physical and chemical methods, which are feasible in terms of wastewater treatment, but tend to be less efficient in fluoride ion removal, requiring a long treatment cycle. Meanwhile, as the conventional fluorine removing agent is adopted in the treatment of the existing fluorine-containing wastewater of the lithium battery, the main concern is fluorine ions, and other harmful substances such as heavy metal ions, organic solvent residues and the like are also contained in the lithium battery wastewater besides the fluorine ions. When aiming at lithium electric wastewater treatment, the removal and treatment of other pollutants are comprehensively considered so as to ensure the final wastewater treatment effect.
Therefore, the development of the efficient defluorination medicament which can effectively remove fluorine and remove other pollutants in lithium electric wastewater has important significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide the medicament which can remove fluorine efficiently and treat other pollutants in lithium battery wastewater.
In order to solve the technical problems, the invention provides a high-efficiency defluorination medicament suitable for lithium electric wastewater, which comprises hydroxyapatite, polyaluminum chloride and H 2 O 2 A redox-type microorganism and a filler, wherein the filler is a porous material having a cyclodextrin derivative supported on the surface, the cyclodextrin derivative comprises carboxylated cyclodextrin, the porous material is an aluminum-containing Metal-organic framework material (Metal-Organic Frameworks, MOFs), and the redox-type microorganism comprises iron-reducing bacteria.
In the invention, the hydroxyapatite is taken as a main fluoride ion adsorbent, and has a large number of surface active sites, so that the hydroxyapatite can rapidly and efficiently adsorb fluoride ions in water, and the fluoride ions can form a complex or charge adsorption on the surface of the calcium hydroxyphosphate and be fixed in the lattice structure of the calcium hydroxyphosphate; meanwhile, calcium ions and fluoride ions generate solid impurities such as calcium fluoride precipitates, and the calcium hydroxy phosphate adsorbed with the fluoride ions can be regenerated by heat treatment, an acid-base elution method and the like.
The polyaluminium chloride is used as a flocculating agent in the defluorination medicament, and generated suspended matters (such as lithium iron phosphate and the like) and small particles such as colloid particles can be aggregated into larger agglomerates, so that the sedimentation speed and separation efficiency of the suspended matters are improved, meanwhile, the heavy metal ions in lithium electric wastewater can be removed in an auxiliary manner, aluminum ions can be subjected to complexation reaction with the heavy metal ions to form insoluble complexes, so that the heavy metal ions are removed, and meanwhile, aluminum ions can also react with fluorine ions to form aluminum fluoride precipitates, so that the fluorine ions are removed in an auxiliary manner.
Aluminum-containing MOFs materials generally have higher chemical stability, can maintain the structural integrity and adsorption performance under wide working conditions, can stably remove fluoride ions for a long time, and meanwhile, aluminum is a relatively cheap and abundant metal element, is lower in cost compared with other noble metals or rare metals, does not contain toxic or environmentally-sensitive elements, and is more environment-friendly.
The lithium electric wastewater contains a large amount of ferrous ions and/or Ni 2+ 、Mn 2+ Ferrous ions and/or Ni existing in hydrogen peroxide and lithium electric wastewater are utilized 2+ 、Mn 2+ Forming Fenton or Fenton-like reagent, activating H by ferrite and the like 2 O 2 After that, the high-activity hydroxyl with strong oxidizing property is formed, and organic matters contained in the lithium electric wastewater are removed through Fenton reaction(s), so that the COD value of the lithium electric wastewater is reduced, and the treated water is more environment-friendly. Meanwhile, the original metal ions in the lithium battery wastewater are fully utilized, the production cost is saved, the requirements on reaction conditions and equipment are lower, the equipment maintenance is simple, the energy consumption is low, and the wastewater treatment cost is reduced.
The iron reducing bacteria reduce iron ions in the solution into ferrous ions, so that ferrous ion regeneration is accelerated, heterotrophic microorganisms such as the iron reducing bacteria mediate synergistic action to accelerate the degradation speed of pollutants in the wastewater, and meanwhile, organic matters, phosphorus and the like in the lithium battery wastewater can be used as nutrient substances of bacteria to promote the growth and metabolic activity of the microorganisms, increase the quantity and activity of the microorganisms and improve Fenton-like reaction effects. Other oxidation-reduction heterotrophic microorganisms can be added to cooperatively promote the degradation of pollutants in the wastewater.
The cyclodextrin derivative in the composite material is loaded on the surface of the porous material through electrostatic adsorption and the like, hydroxyl groups or carboxyl groups and the like on the cyclodextrin derivative are stably loaded in the porous material, so that the porous material can be prevented from being separated from the porous material in the wastewater treatment process to generate new pollution, meanwhile, the porous material has more pore channels, so that the cyclodextrin derivative has larger specific surface area and richer pore structure and more adsorption sites, the adsorption quantity of the cyclodextrin derivative to organic matters (such as acetone, ethyl acetate and citric acid) can be cooperatively improved in the lithium electric wastewater removal process, meanwhile, the pore channel structure is also favorable for loading of microorganisms, and the adsorbed organic matters can also be used as a carbon source of microorganisms, so that the integral purification effect of the lithium electric wastewater is improved.
In one embodiment of the invention, theHydroxyapatite, polyaluminum chloride, H 2 O 2 The mass parts of the redox microorganism and the filler are 1:0.2 to 0.3:0.3 to 0.5:0.3 to 0.6:0.3 to 0.8. The defluorination medicament with the mass ratio range can better realize defluorination by utilizing the synergistic interaction of the components, and simultaneously, the concentration of other pollutants in the lithium electric wastewater is reduced.
In one embodiment of the invention, the carboxylated cyclodextrin is carboxylated β -cyclodextrin. Other cyclodextrins can be used, and the beta-cyclodextrin has a larger cavity and is wider in source; good adsorption effect and low cost.
In one embodiment of the present invention, the carboxylated cyclodextrin is selected from at least one of carboxymethyl, carboxyethyl or carboxypropyl cyclodextrin.
In one embodiment of the invention, the porous material is at least one of MIL-53 (Al), MOF-303 (Al), NH2-MIL-101 (Al).
In one embodiment of the present invention, the method for preparing the filler comprises the steps of:
dispersing aluminum-containing MOFs into water, adding cyclodextrin derivatives, and stirring or ultrasonic treating.
In one embodiment of the present invention, the method for preparing hydroxyapatite comprises the steps of: mixing the diatom shell with the calcium salt, adding the hydrogen phosphate, controlling the pH of the solution to be 10-11, reacting at 85-95 ℃, drying and calcining to obtain the product. The hydroxyapatite prepared by taking the diatom shell as the template is more natural and environment-friendly, has wide sources, and is more environment-friendly compared with the artificially synthesized template material. The diatom shell is provided with a series of tiny pore canals and pores, the pore canals can provide more diffusion channels and adsorption sites, and the contact area between the hydroxyapatite and fluoride ions in the wastewater is increased, so that the defluorination reaction is promoted. The diatom shells are commercially available and can also be self-made by referring to the prior art.
In one embodiment of the invention, the reaction time is 15 to 36 hours.
In one embodiment of the invention, the calcination temperature is 800 to 1200 degrees celsius.
In one embodiment of the invention, the calcination time is 2 to 10 hours.
In one embodiment of the invention, the pH of the solution is controlled to 10-11 by ammonia.
The invention also provides a lithium battery wastewater treatment process, which comprises the following steps:
s1, regulating the pH value of lithium electric wastewater to 6-9, and adding hydroxyapatite and filler into the lithium electric wastewater;
s2, regulating the pH value of the lithium battery wastewater to be less than 6 (preferably 3-5), and adding H 2 O 2 And a redox species microorganism;
s3, controlling the pH of the wastewater to be 6.5-7.5, and adding polyaluminium chloride.
In some embodiments of the present invention, the pH of the lithium battery wastewater in the step S1 is adjusted to 6-7. Under the condition of partial acidity (pH < 7), the beta-cyclodextrin has better solubility and better adsorption effect.
In some embodiments of the invention, the process further comprises performing a filtering operation after performing step S3.
Compared with the prior art, the technical scheme of the invention has the following advantages: according to the scheme, the raw materials of the defluorination medicament are matched in a synergistic manner, so that the defluorination medicament can be used for efficiently and rapidly removing fluorine, and can be used for treating various pollutants such as organic matters, phosphates, heavy metals and the like in lithium electric wastewater; the hydroxyapatite adsorbs and removes fluorine, the filler assists in adsorbing pollutants such as organic matters, the adsorbed organic matters can be used as a carbon source of microorganisms, meanwhile, a matrix of the filler can be used as an attachment point of the microorganisms, the microorganisms can synergistically accelerate degradation of the pollutants, the treatment efficiency is improved, the produced suspended matters, colloidal particles and other small particles can be aggregated into larger agglomerates by the polyaluminium chloride, meanwhile, the sedimentation speed and the separation efficiency of the suspended matters can be improved, and further, heavy metal ions can be removed in an assisted mode. In the application process, hydroxyapatite, filler, fluorine, organic matters and the like are added, hydrogen peroxide and redox microorganisms are added to further reduce the content of the organic matters, finally polyaluminum chloride is added to remove residual fluorine and calcium fluoride precipitate, and meanwhile heavy metal ions are removed to realize standard discharge of wastewater.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
MOFs materials in the examples below were purchased from sienna ziyue biotechnology limited. ZIF-8, product number Q-0272500, NH 2 MIL-101 (Al) accession number Q-0039706, MIL-53 (Al) accession number Q0259817. Unless otherwise specified, all reagents used were commercially available analytically pure grade reagents. The hydrogen peroxide is added in the form of hydrogen peroxide stock solution obtained in the market, and the dosage is H 2 O 2 Quality.
The embodiment of the invention provides a high-efficiency defluorination medicament suitable for lithium battery wastewater, and the formula and the weight parts of the high-efficiency defluorination medicament are shown in the following table 1.
TABLE 1
The preparation method of hydroxyapatite in example 1 and examples 4 to 7 is as follows:
the diatom shell and calcium salt (calcium chloride) are mixed according to the mass ratio of 1:2, mixing, and mixing with calcium ions in calcium salt according to the molar ratio of 4:1, adding hydrogen phosphate (ammonium hydrogen phosphate), controlling the pH of the solution to be 10.5 by ammonia water, reacting at 90 ℃ for 30 hours, drying at 60 ℃, and calcining at 1000 ℃ for 5 hours.
The preparation process of the diatom shell comprises the following steps: (1) Removing supernatant in the culture container of the navicular algae, scraping benthic navicular algae on the container wall, and obtaining the navicular algae concentrated solution.
(2) Adding hydrochloric acid with the mass fraction of 15% into the navicular concentrated solution treated in the first step, stopping the reaction of the hydrochloric acid and the diatom when the diatom does not generate bubbles any more, and obtaining a mixture I, wherein the volume ratio of the navicular concentrated solution to the hydrochloric acid is 1:9.
(3) The mixture I was centrifuged at 8000rpm and the supernatant was removed to obtain a mixture II.
(4) Adding deionized water into the mixture II for cleaning according to the following ratio of 1:20, and centrifuging at 9000rpm after washing, and removing the supernatant to obtain a mixture III.
(5) Repeating the cleaning of the operation (4) for 5 times, placing the obtained mixture into an oven, preserving heat for 12 hours at 100 ℃, heating to 700 ℃ at a heating rate of 1 ℃/min after the moisture in the mixture is dried, and preserving heat for 3 hours in an air atmosphere to obtain the composite material.
The hydroxyapatite in example 2 is commonly commercially available from aatin under cas No. 1306-06-5.
The procedure for the preparation of hydroxyapatite in example 3 differs from that of example 1 in that: the template used was bovine serum albumin (available from Allatin, cas No. 9048-46-8).
Examples 1 to 3 and 5 to 7 were NH supported on carboxymethyl-beta-cyclodextrin as filler 2 MIL-101 (Al) prepared by reacting NH 2 Ultrasonic dispersing MIL-101 (Al) in water, adding NH 2 And (3) carrying out ultrasonic treatment on carboxymethyl-beta-cyclodextrin with the mass of 3 times of MIL-101 (Al) for 24 hours to obtain the product.
The filler in example 4 is MIL-53 (Al) loaded with carboxymethyl-beta-cyclodextrin, and the preparation process comprises the steps of dispersing MIL-53 (Al) into water by ultrasonic, adding carboxymethyl-beta-cyclodextrin with the mass 3 times of that of MIL-53 (Al), and carrying out ultrasonic treatment for 24 hours.
The redox microorganism of examples 1 to 7 was an iron-reducing bacterium, commercially available, specifically Shewanellapiezotolerans WP3 of the genus Shewanella, added as a culture broth, wherein the Shewanellapiezotolerans WP strain had a concentration of 10 6 CFU/ml to 10 7 CFU/ml。
The comparative example of the present invention provides a defluorinating agent with the formulation shown in table 2.
TABLE 2
The amount of the substance of calcium in the calcium chloride in comparative example 2 was equal to the amount of the substance of hydroxyapatite in comparative example 1.
The porous material of the filler in comparative example 5 was ZIF-8.
The preparation method of hydroxyapatite in comparative examples 1 and 2 to 6 was the same as in example 1. The filler preparation process of comparative examples 1 to 5 is the same as in example 1.
The redox microorganism of comparative examples 1 to 3 and 5 to 6 was iron-reducing bacteria, commercially available as Shewanellapiezotolerans WP3 of Shewanella, and was added as a culture solution, wherein the Shewanellapiezotolerans WP strain 3 had a concentration of 10 6 CFU/ml to 10 7 CFU/ml。
The high-efficiency defluorination medicaments in the examples 1-7 and the comparative examples 1-6 are added into the wastewater of a certain lithium electricity recovery factory according to the proportion of 1kg to 1L, and the specific adding process is as follows:
s1, firstly, regulating the pH value of wastewater to 6.5+/-0.2, adding hydroxyapatite and a filler (if the wastewater does not contain the hydroxyapatite, the hydroxyapatite is replaced by a mixture of activated carbon and calcium chloride in the scheme of comparative example 2), and stirring and reacting for 4 hours at the speed of 300rpm at the temperature of 55 ℃;
s2, regulating the pH value to 4.0+/-0.2, adding hydrogen peroxide and redox microorganisms (if not, adding the hydrogen peroxide and the redox microorganisms), and stirring at 300rpm for reaction for 5 hours;
s3, controlling the pH of the wastewater to be 7.0+/-0.2, adding polyaluminium chloride, and filtering to remove the precipitate after the precipitation is complete.
The wastewater components before adding the defluorinating agent were measured by ICP method (COD value was measured by COD detector) as shown in table 3 below:
TABLE 3 Table 3
| Composition of the components | Total iron | Total nickel | Total cobalt | Total manganese | F - | COD |
| Concentration (g/L) | 34.253 | 12.532 | 2.379 | 3.747 | 3.878 | 0.345 |
The compositions of the wastewater treated by examples 1 to 7 or comparative examples 1 to 6 are shown in the following table 4:
TABLE 4 Table 4
As can be seen from the above table, the scheme of the invention can be adopted to enable F - The content is reduced by more than 90 percent, and the total content of heavy metal ions such as iron, cobalt, nickel and the likeThe COD value is reduced to below 154mg/L by more than 70%, and the emission standard is met. Therefore, the scheme of the invention can remove fluorine efficiently, and simultaneously can effectively reduce heavy metal ions and COD value in wastewater so that the wastewater can reach the dischargeable standard.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The utility model provides a high-efficient defluorination medicament suitable for lithium electricity waste water which characterized in that: comprises hydroxyapatite, polyaluminum chloride and H 2 O 2 The filler is a porous material with a cyclodextrin derivative loaded on the surface, the cyclodextrin derivative comprises carboxylated cyclodextrin, the porous material is MOFs containing aluminum, and the redox microorganism comprises iron reducing bacteria.
2. The high efficiency defluorinating agent according to claim 1, wherein: the hydroxyapatite, polyaluminum chloride and H 2 O 2 The mass parts of the redox microorganism and the filler are 1:0.2 to 0.3:0.3 to 0.5:0.3 to 0.6:0.3 to 0.8.
3. The high efficiency defluorinating agent according to claim 1, wherein: the carboxylated cyclodextrin is carboxylated beta-cyclodextrin.
4. The high efficiency defluorinating agent according to claim 1, wherein: the carboxylated cyclodextrin is at least one selected from carboxymethyl, carboxyethyl or carboxypropyl cyclodextrin.
5. The high efficiency defluorinating agent according to claim 1, wherein: the porous material is at least one of MIL-53 (Al), MOF-303 (Al) and NH2-MIL-101 (Al).
6. The high efficiency defluorinating agent according to claim 1, wherein: the preparation method of the filler comprises the following steps: dispersing aluminum-containing MOFs into water, adding cyclodextrin derivatives, and stirring or ultrasonic treating.
7. The high efficiency defluorinating agent according to claim 1, wherein: the preparation method of the hydroxyapatite comprises the following steps: mixing the diatom shell with the calcium salt, adding the hydrogen phosphate, controlling the pH of the solution to be 10-11, reacting at 85-95 ℃, drying and calcining to obtain the product.
8. The high efficiency defluorinating agent as claimed in claim 7, wherein: the pH of the solution is controlled to be 10-11 by ammonia water.
9. A process for treating lithium electrical wastewater using the high efficiency defluorinating agent according to any one of claims 1 to 8, characterized in that: the method comprises the following steps: s1, regulating the pH value of lithium electric wastewater to 6-9, and adding hydroxyapatite and filler into the lithium electric wastewater; s2, regulating the pH value of lithium battery wastewater to be less than 6, and adding H 2 O 2 And a redox species microorganism; s3, controlling the pH of the wastewater to be 6.5-7.5, and adding polyaluminium chloride.
10. The process according to claim 9, characterized in that: and in the step S2, the pH value of the lithium battery wastewater is regulated to 3-5.
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