CN114053992A - Composite material for deeply removing fluorine ions in wastewater, preparation method and application - Google Patents
Composite material for deeply removing fluorine ions in wastewater, preparation method and application Download PDFInfo
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- CN114053992A CN114053992A CN202010744586.8A CN202010744586A CN114053992A CN 114053992 A CN114053992 A CN 114053992A CN 202010744586 A CN202010744586 A CN 202010744586A CN 114053992 A CN114053992 A CN 114053992A
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- composite material
- wastewater
- hydroxide
- zirconium
- fluorine ions
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- -1 fluorine ions Chemical class 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 68
- 239000011737 fluorine Substances 0.000 title claims abstract description 68
- 239000002351 wastewater Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 30
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 238000010335 hydrothermal treatment Methods 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 17
- 150000003754 zirconium Chemical class 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 11
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 abstract description 11
- 238000010668 complexation reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 abstract 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 26
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 26
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 24
- 238000003756 stirring Methods 0.000 description 16
- 239000008399 tap water Substances 0.000 description 15
- 235000020679 tap water Nutrition 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 230000006872 improvement Effects 0.000 description 13
- 229910001629 magnesium chloride Inorganic materials 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000701 coagulant Substances 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 230000003311 flocculating effect Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000011698 potassium fluoride Substances 0.000 description 5
- 235000003270 potassium fluoride Nutrition 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000003745 diagnosis Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 230000008520 organization Effects 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
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- 235000010755 mineral Nutrition 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical class [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 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 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
-
- 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
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
-
- 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
- C02F2101/105—Phosphorus compounds
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the field of sewage treatment, and discloses a composite material for deeply removing fluorine ions in wastewater, a preparation method and application thereof. The layered composite metal hydroxide is used for adsorbing and removing fluoride ions and other high-valence anions in the wastewater, the strong complexation of the aluminum hydroxide, the zirconium hydroxide and the fluoride ions is used for removing the fluoride ions, the aim of deeply removing the fluoride ions in the wastewater is fulfilled by the synergy of the components, the problems of high cost, slow sedimentation rate and large generation amount of solid waste of the existing method are solved, the material disclosed by the invention can be applied in a wider pH range, the pH of the wastewater does not need to be adjusted to be lower than 4, the application range is greatly widened, the treatment cost is reduced, and the popularization is facilitated.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a composite material for deeply removing fluorine ions in wastewater, and preparation and application thereof.
Background
Fluoride is a common contaminant in water and long-term fluorine exposure can lead to fluorosis [ Jadhav S.V., Bringas E., Yadav G.D., Rathod V.K., Ortiz I., Marathe K.V.arsenic and fluoride associated groups waters: a review of current technologies for contaminants removal. journal of Environmental management 2015,162, 306-; mohapatra m, Anand s, Mishra b.k., Giles d.e., Singh p.review of fluoride removal from driving water. journal of Environmental management 2009,91,67-77]. The world health organization stipulates that fluorine in drinking water must be less than 1.5mg L-1[World Health Organization(WHO),2011.Guidelines for Drinking Water Quality,fourth ed]. Various methods have been developed to remove fluorine from water, such as chemical precipitation, coagulation, electrocoagulation, adsorption, ion exchange and membrane filtration. Many metal oxides and hydroxides, such as aluminum and zirconium oxides, are reported to be effective adsorbents for fluoride ions. For better engineering applications, zirconium hydroxide/oxide is supported on different carriers, such as collagen fibers, carboxymethyl cellulose, β -cyclodextrin and hollow fiber membranes. One common disadvantage of these zirconium-based adsorbents is thatThe pH adaptability is poor. For effective removal of F, it is generally necessary to use acidic conditions (pH of about 3.0) [ Gan Y., Wang X., Zhang L., Wu B., Zhang G., Zhang S.Coagulant removal of fluoride by zirconium tetrachloride: Performance evaluation and mechanism analysis. Chemosphere.2019,218, 860-868).]。
The decrease in solution pH is a natural result of the hydrolysis of the metal salt coagulant. Thus, coagulation can better meet the pH requirement for fluorine removal. Aluminum-based coagulants are reported to have strong defluorination ability [ Ingallinella A.M., Pacini V.A., Fernandez R.G., Vidoni R.M., Sanguin G.Simulanous removal of inductive and fluoride from group water by interaction-adsorption with a polymeric chloride. journal of Environmental Science and Health Part A,2011,46, 1288-. However, the formation of aluminum-fluorine complexes significantly inhibits the hydrolysis of aluminum salts [ Liu R.P., Liu B., Zhu L.J., He Z., Ju J.W., Lan H.C., Liu H.J.effects of fluorine on the removal of calcium and phosphate by aluminum complex. journal of Environmental sciences.2015,32,118-125 ]. As a result, the residual concentrations of aluminum and fluorine cannot reach the prescribed limits [ Yu W.Z., growth J., Graham N.Regrowth of branched hydroxide flows: effect of added fluoride. environmental Science and technology 2016.50, 1828-1833 ]. Further measures need to be taken to remove the residual aluminium. In addition, aluminum salts coagulate to produce harmful sludge, which is difficult to dispose of [ Gan y., Wang x., Zhang l., Wu b., Zhang g., Zhang s. coaggulant removal of fluoride by zirconium tetrachloride: Performance evaluation and mechanism analysis. chemisphere.2019, 218, 860-868 ].
For decades, zircon salt has been widely used as a coagulant for water treatment, and inorganic zircon salt coagulants are effective in removing organic materials, thereby minimizing the generation of disinfection by-products [ Jarvis p., Sharp e., Pidou m., Molinder r., Parsons s.a., Jefferson b.2012.com. diagnosis of diagnosis performance and flow properties use a novel zirconium complex diagnosis and quality diagnosis. water research.2012,46, 4179-; fast tracking the molecular weight changes of magnetic substructures in conjugation/hybridization processes via fluorescence EEM-PARAFAC, Chemosphere.2017,178, 317-. In addition, the zirconium salt flocs are larger than aluminum coagulants, and are more favorable for subsequent membrane filtration [ Su Z.Y., Li X., Yang Y.L., Fan Y.R. binding the application of a zirconium complex in a conjugation-ultrafiltration process: microorganisms on organic removal and membrane filtration RSC Advances.2017, 329 42338 ]. Gan et al used zirconium tetrachloride to remove fluoride ions from wastewater and found that fluoride ions could be removed efficiently and flocculated and precipitated, but the optimum reaction condition was pH 4, and the applicable condition was easily limited by pH.
Based on the defects of the prior art, it is highly desirable to invent a new material and method capable of deeply removing fluorine ions.
Disclosure of Invention
1. Problems to be solved
In the prior art, aiming at the problem of poor deep removal effect of fluorine ions in a water body, the layered composite metal hydroxide containing 3 or more metal types of zirconium hydroxide is prepared by a hydrothermal method, fluorine ions and other high-valence anions in wastewater are removed by utilizing the layered composite metal hydroxide through ion exchange, meanwhile, the fluorine ions are removed in a targeted manner by utilizing the strong complexation of the zirconium hydroxide doped in a composite structure and the fluorine ions, and in the treatment process, the removal of the other high-valence anions by the layered composite metal hydroxide reduces the competition of the complexation between the fluorine ions and the zirconium hydroxide, so that the purpose of deeply removing the fluorine ions in the wastewater is achieved.
Furthermore, aiming at the problems that the zirconium hydroxide/oxide is loaded on different carriers and has poor pH adaptability and generally needs to use acidic conditions (the pH value is about 3.0) and the problem that the zirconium salt is used for removing fluorine and is limited by the condition of low pH (the pH value is less than or equal to 4), the material provided by the invention does not need to be limited by a low pH environment in the application process and has a wide application range.
Further, aiming at the problem that the aluminum-based coagulant is easy to cause pollution, the composite material prepared by the invention can not be dissolved into a water body to cause secondary pollution by stably fixing the zirconium hydroxide and other metal hydroxides in the crystal lattice of the synthetic mineral, so that the composite material has better environment friendliness.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a composite material for deeply removing fluorine ions in wastewater, which is a layered composite metal hydroxide at least containing 3 metal hydroxides prepared by a hydrothermal method, wherein the layered composite metal hydroxide contains zirconium hydroxide.
As a further improvement of the present invention, the layered composite metal hydroxide contains zirconium hydroxide and aluminum hydroxide.
As a further improvement of the present invention, the layered composite metal hydroxide contains zirconium hydroxide, magnesium hydroxide and aluminum hydroxide.
As a further improvement of the invention, the preparation method of the composite material for deeply removing the fluorine ions in the wastewater comprises the following steps:
1) preparing a mixed solution containing at least 3 metal ions, wherein the mixed solution contains zirconium ions;
2) dropwise adding a sodium hydroxide solution into the mixed solution to obtain a slurry-like substance;
3) centrifuging the slurry-like substance, washing with pure water, and centrifuging again to obtain a solid substance;
4) carrying out hydrothermal treatment, freeze drying, grinding into powder and sieving on the solid obtained in the step 3) to obtain the composite material.
As a further improvement of the invention, the preparation process in the step 1) comprises the following steps: mixing magnesium salt, aluminum salt and zirconium salt to obtain a mixture, and adding water to dissolve the mixture to obtain a mixed solution; the added mass of the zirconium salt is not less than 5 percent of the total mass of the mixture.
As a further improvement of the invention, the added mass of the zirconium salt in the step 1) accounts for 5-30% of the total mass of the mixture.
As a further improvement of the invention, the amount of the substance of the sodium hydroxide is not less than 3 times of the total amount of the substances of magnesium, aluminum and zirconium.
As a further improvement of the invention, the centrifugation speed in the step 3) is 5000-10000 rpm.
As a further improvement of the invention, the temperature of the hydrothermal treatment in the step 4) is not lower than 60 ℃, and the treatment time is not less than 60 minutes.
As a further improvement of the invention, the temperature of the hydrothermal treatment is 105 ℃ and the time is 240 minutes.
As a further improvement, the invention provides an application method of the composite material for deeply removing the fluorine ions in the wastewater, and the composite material is added into the fluorine-containing wastewater to remove the fluorine ions in the wastewater.
As a further improvement of the invention, the concentration of the composite material in the wastewater is not lower than 5 mg/L.
As a further improvement of the invention, the concentration of the composite material in the wastewater is not lower than 25 mg/L.
As a further improvement of the invention, the pH value of the waste water is less than or equal to 6.
In the preferable scheme, the fluoride ions in the wastewater are removed by firstly stirring at a high speed and then stirring at a low speed to perform sedimentation removal of the fluoride ions.
In the preferred scheme, during the process of removing the fluoride ions in the wastewater, the wastewater is firstly rapidly stirred for 2 minutes, then slowly stirred for 15 minutes, and then settled for 15 minutes.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the composite material for efficiently removing the fluorine ions in the wastewater is prepared by a hydrothermal method, namely the layered composite metal hydroxide containing 3 or more metal types of zirconium hydroxide has high selectivity for the fluorine ions, and solves the problem that the low-concentration fluorine ions are difficult to remove. Thereby obviously improving the selective complexing effect of the zirconium hydroxide and the fluorine ions, and the synergistic effect of the zirconium hydroxide and the fluorine ions obviously improves the removing effect of the composite material on the fluorine ions.
(2) The composite material for efficiently removing the fluoride ions in the wastewater also contains aluminum hydroxide, and strong complexation exists between the aluminum hydroxide and the fluoride ions, and the removal of the layered composite metal hydroxide to other high-valence anions in the treatment process reduces the competition of the complexation between the fluoride ions and zirconium hydroxide and aluminum hydroxide, thereby achieving the purpose of deeply removing the fluoride ions in the wastewater.
(3) The layered composite metal hydroxide containing 3 or more metal types of zirconium hydroxide prepared by the composite material for efficiently removing fluorine ions in wastewater is regular cube or hexagon in structure, has larger specific surface area and larger adsorption capacity compared with the layered double hydroxide with the original cuboid structure, and is more beneficial to removing the fluorine ions.
(4) The composite material for efficiently removing the fluoride ions in the wastewater has the advantages of environmental friendliness, small influence on the physicochemical property of the wastewater, obvious economic benefit and application value, and can stably fix the zirconium hydroxide in the crystal lattice of the synthetic mineral without dissolving into the water body to cause secondary pollution.
(5) The method for deeply removing the fluorine ions in the water body by using the composite material widens the application range of the material, the application process of the material is not limited by the condition of low pH, the composite is better used in the water body with the pH being less than or equal to 6, the hydrolysis degree of the water body with the pH being less than or equal to 6 is relatively low, and the competitive effect of anions is reduced, so that zirconium hydroxide in the composite material has more fluorine ion coordination sites, and the superior fluorine removal effect is realized.
Drawings
FIG. 1 is a schematic structural view of a zirconium-doped layered composite metal hydroxide;
FIG. 2 is a transmission electron microscopy characterization comparison of the zirconium doped layered double metal hydroxide of example 1 with layered double metal hydroxide alone;
FIG. 3 is a graph showing the effect of 5% zirconium in the composite material of example 2 on the removal of various concentrations of fluoride ions;
FIG. 4 is a graph showing the effect of a composite material of example 3 containing 20% zirconium on the removal of various concentrations of fluoride ions;
FIG. 5 is a graph showing the effect of 30% zirconium in the composite material of example 4 on the removal of various concentrations of fluoride ions;
FIG. 6 is a graph showing the effect of the composite material containing 30% zirconium in example 5 on the deep removal of fluorine ions from photovoltaic wastewater;
FIG. 7 is a graph showing the removal effect of the layered double hydroxide prepared in comparative example A on different concentrations of fluoride ions;
FIG. 8 is a graph showing the effect of adding zirconium salt on the removal of fluoride ions at different concentrations in comparative example B.
Detailed Description
The invention is further described with reference to specific examples.
It should be noted that the terms "upper", "lower", "left", "right" and "middle" used in the present specification are for the sake of clarity, and are not intended to limit the scope of the present invention, and changes or adjustments of the relative relationship thereof may be made without substantial technical changes.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, measure or value. The degree of flexibility for a particular variable can be readily determined by one skilled in the art.
As used herein, at least one of the terms "is intended to be synonymous with one or more of. For example, "at least one of A, B and C" explicitly includes a only, B only, C only, and combinations thereof, respectively.
Concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limit values of 1 to about 4.5, but also include individual numbers (such as 2,3, 4) and sub-ranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed to include all of the aforementioned values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or feature being described.
Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims.
The invention is further described with reference to specific examples.
Example 1
The synthesis method of the zirconium-doped layered composite hydroxide for deeply removing the fluoride ions in the wastewater comprises the following steps:
1) respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; wherein, the zirconium chloride is added with 5 to 30 percent of the total mass of the mixture by mass, the mixture is stirred on a stirrer after being added with water and stirred evenly until the zirconium chloride is completely dissolved to form a mixed solution, and the concentrations of the magnesium chloride, the aluminum chloride and the zirconium chloride in the mixed solution are 285mg/L, 133mg/L and 21mg/L respectively.
2) Dissolving sodium hydroxide in water to obtain a 6g/L sodium hydroxide solution, dropwise adding the sodium hydroxide solution into the mixed solution of the magnesium salt, the aluminum salt and the zirconium salt to obtain a slurry-like substance, wherein the added amount of the sodium hydroxide substance is not less than 3 times of the sum of the amounts of the magnesium salt, the aluminum salt and the zirconium salt.
3) Centrifuging the slurry-like substance at 5000-10000 rpm, and washing with pure water for three times. And after washing, carrying out hydrothermal treatment, wherein the time of the hydrothermal treatment is not less than 60 ℃, and the treatment time is not less than 60 minutes. And (4) freeze-drying the sample after the hydrothermal treatment, grinding the sample into powder, and sieving, sealing and storing the composite material. FIG. 1 is a schematic structural diagram of the finally prepared zirconium-doped layered composite metal hydroxide.
While separately synthesizing a layered double hydroxide (zirconium undoped) as a comparison, the procedure for the separate synthesis is essentially the same as the above method except that: no zirconium salt was added in step 1).
FIG. 2 is a comparative graph of transmission electron microscopy characterization of zirconium-doped layered double metal hydroxide (LDH-Zr) versus layered double metal hydroxide (LDH) alone in example 1; as can be seen from a comparison of fig. 2, the layered double hydroxide prepared separately is a regular cuboid, while the zirconium-doped layered composite metal hydroxide has a regular cubic or hexagonal structure.
Example 2
The embodiment firstly prepares the composite material, and then adopts the composite material to deeply remove the fluorine ions in the wastewater, and the steps are as follows:
1) respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; wherein, the zirconium chloride is added with 5 percent of the total mass of the mixture by mass, and after being added with water and stirred evenly, the mixture is placed on a stirrer and stirred until being completely dissolved to obtain mixed solution; the concentrations of magnesium chloride, aluminum chloride and zirconium chloride in the mixed solution are 285mg/L, 133mg/L and 21mg/L respectively.
2) Weighing sodium hydroxide, dissolving the sodium hydroxide in water to obtain a sodium hydroxide solution, and dropwise adding 6g/L of the sodium hydroxide solution into a mixed solution containing magnesium salt, aluminum salt and zirconium salt, wherein the amount of the sodium hydroxide is not less than 3 times of the sum of the amounts of magnesium, aluminum and zirconium, so as to obtain a slurry-like substance. Centrifuging the slurry-like substance at 5000-10000 rpm, and washing with pure water for three times. After the completion of the washing, hydrothermal treatment was carried out (treatment temperature: 105 ℃ C., treatment time: 240 minutes). And (4) freeze-drying the sample after the hydrothermal treatment, grinding the sample into powder, and sieving, sealing and storing the composite material.
3) The potassium fluoride is dissolved in Nanjing tap water, the pH of the Nanjing tap water is 7.6, and the types and concentrations of anions are shown in Table 1.
TABLE 1 concentration of anions from tap water
| Cl-(mg/L) | SO4 2-(mg/L) | NO3 -(mg/L) | PO4 3-(mg/L) |
| 1.52 | 1.90 | 0.29 | 1.32 |
Initial concentrations of 2.5, 5.0, 10.0 and 15.0mg/L fluoride ion solutions were prepared as described above. Adding hydrochloric acid to adjust the pH value of the fluorine-containing tap water to be below 6, adding 50mg/L of the composite material, quickly stirring for 2 minutes, then slowly stirring for 15 minutes, flocculating and settling for 15 minutes, and then measuring the concentration of fluorine ions in the supernatant by using a fluorine ion selective electrode.
From the results, it is known that the removal rates of the composite material for the fluoride ions with different concentrations are 65%, 64%, 63% and 65%, respectively, and the removal results of the fluoride ions are shown in fig. 3, and the removal rate of the fluoride ions is more than 60%.
According to the invention, the larger the adding amount of the zirconium-doped layered composite metal hydroxide is, the better the fluorine ion depth removal effect is.
Example 3
The embodiment firstly prepares the composite material, and then adopts the composite material to deeply remove the fluorine ions in the wastewater, and the steps are as follows:
1) respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; wherein the zirconium chloride is added with the mass accounting for 20 percent of the total mass of the mixture, the zirconium chloride is added with water and stirred evenly, and then the mixture is placed on a stirrer and stirred until the zirconium chloride is completely dissolved to obtain a mixed solution, and the concentrations of the magnesium chloride, the aluminum chloride and the zirconium chloride in the mixed solution are 285mg/L, 133mg/L and 105mg/L respectively.
2) Weighing sodium hydroxide, dissolving the sodium hydroxide in water to obtain a sodium hydroxide solution, and dropwise adding 6g/L of the sodium hydroxide solution into a mixed solution of magnesium salt, aluminum salt and zirconium salt, wherein the amount of the sodium hydroxide is not less than 3 times of the sum of the amounts of magnesium, aluminum and zirconium to obtain a slurry-like substance. Centrifuging the slurry-like substance at 5000-10000 rpm, and washing with pure water for three times. After the washing, hydrothermal treatment (105 ℃ C., 240 minutes) was carried out. And (4) freeze-drying the sample after the hydrothermal treatment, grinding the sample into powder, and sieving, sealing and storing the composite material.
(2) The potassium fluoride is dissolved in Nanjing tap water, the pH of the Nanjing tap water is 7.6, and the types and concentrations of anions are shown in Table 1. Preparing initial fluorine ion solutions with the concentrations of 2.5, 5.0, 10.0 and 15.0 mg/L. Adding hydrochloric acid to adjust the pH value of the fluorine-containing tap water to be below 6, adding 50mg/L of the composite material, quickly stirring for 2 minutes, then slowly stirring for 15 minutes, flocculating and settling for 15 minutes, and then measuring the concentration of fluorine ions in the supernatant by using a fluorine ion selective electrode.
From the results, it is known that the removal rates of the composite material for fluorine ions with different concentrations are 77%, 78%, 77% and 73%, respectively, and the removal results of fluorine ions are shown in fig. 4, and the removal rate of fluorine ions is more than 70%.
According to the invention, the larger the adding amount of the zirconium-doped layered composite metal hydroxide is, the better the fluorine ion depth removal effect is.
Example 4
The embodiment firstly prepares the composite material, and then adopts the composite material to deeply remove the fluorine ions in the wastewater, and the steps are as follows:
1) respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; wherein the zirconium chloride is added with 30 percent of the total mass of the mixture by mass, the mixture is added with water and stirred evenly, and then the mixture is placed on a stirrer to be stirred until the zirconium chloride is completely dissolved, so as to obtain a mixed solution, and the concentrations of the magnesium chloride, the aluminum chloride and the zirconium chloride in the mixed solution are 285mg/L, 133mg/L and 179mg/L respectively.
2) Weighing sodium hydroxide, dissolving the sodium hydroxide in water to obtain a sodium hydroxide solution, and dropwise adding 6g/L of the sodium hydroxide solution into a mixed solution of magnesium salt, aluminum salt and zirconium salt, wherein the amount of the sodium hydroxide is not less than 3 times of the sum of the amounts of magnesium, aluminum and zirconium to obtain a slurry-like substance. Centrifuging the slurry-like substance at 5000-10000 rpm, and washing with pure water for three times. After the washing, hydrothermal treatment (105 ℃ C., 240 minutes) was carried out. And (4) freeze-drying the sample after the hydrothermal treatment, grinding the sample into powder, and sieving, sealing and storing the composite material.
3) The potassium fluoride is dissolved in Nanjing tap water, the pH of the Nanjing tap water is 7.6, and the types and concentrations of anions are shown in Table 1. Preparing initial fluorine ion solutions with the concentrations of 2.5, 5.0, 10.0 and 15.0 mg/L. Adding hydrochloric acid to adjust the pH value of the fluorine-containing tap water to be below 6, adding 50mg/L of the composite material, quickly stirring for 2 minutes, then slowly stirring for 15 minutes, flocculating and settling for 15 minutes, and then measuring the concentration of fluorine ions in the supernatant by using a fluorine ion selective electrode.
From the results, it is known that the removal rates of the composite material for the fluoride ions with different concentrations are respectively 84%, 85%, 83% and 78%, and the removal results of the fluoride ions are shown in fig. 5, and the removal rate of the fluoride ions is more than 78%.
Example 5
The embodiment firstly prepares the composite material, and then adopts the composite material to deeply remove the fluorine ions in the wastewater, and the steps are as follows:
1) respectively adding magnesium chloride, aluminum chloride and zirconium chloride into a beaker, and mixing to obtain a mixture; wherein the zirconium chloride is added with 30 percent of the total mass of the mixture by mass, the mixture is added with water and stirred evenly, and then the mixture is placed on a stirrer to be stirred until the zirconium chloride is completely dissolved, so as to obtain a mixed solution, and the concentrations of the magnesium chloride, the aluminum chloride and the zirconium chloride in the mixed solution are 285mg/L, 133mg/L and 179mg/L respectively.
2) Weighing sodium hydroxide, dissolving the sodium hydroxide in water to obtain a sodium hydroxide solution, and dropwise adding 6g/L of the sodium hydroxide solution into a mixed solution of magnesium salt, aluminum salt and zirconium salt, wherein the amount of the sodium hydroxide is not less than 3 times of the sum of the amounts of magnesium, aluminum and zirconium to obtain a slurry-like substance. Centrifuging the slurry-like substance at 5000-10000 rpm, and washing with pure water for three times. After the washing, hydrothermal treatment (105 ℃ C., 240 minutes) was carried out. And (4) freeze-drying the sample after the hydrothermal treatment, grinding the sample into powder, and sieving, sealing and storing the composite material.
(2) Photovoltaic wastewater is collected, and the concentration of fluorine ions is determined to be 3.2mg/L, and the pH value of the water body is 8.5. Firstly, adjusting the pH value of the wastewater to be below 6, adding zirconium-doped layered composite metal hydroxide (10, 25, 50, 75 and 100mg/L) with different concentrations, quickly stirring for 2 minutes, then slowly stirring for 15 minutes, flocculating and settling for 15 minutes, and then measuring the concentration of fluorine ions in the supernatant by using a fluorine ion selective electrode. Three parallel groups were performed, and the removal results of fluoride ions are shown in FIG. 6, and the removal rates were 41%, 58%, 79%, 87%, and 92%, respectively. When more than or equal to 50mg/L of zirconium-doped layered composite metal hydroxide is added, the concentration of fluorine ions can be reduced to below 1.0 mg/L, and the emission standard of the world health organization is met.
Comparative example A
This comparative example is the result of the preparation of a single layered double hydroxide and the removal of fluoride ion adsorption, and the procedure for the preparation of a layered double hydroxide is essentially the same as in example 1, except that: step 1) without introducing zirconium chloride, specifically as follows:
(1) respectively adding magnesium chloride and aluminum chloride into a beaker, adding water, stirring uniformly, and stirring on a stirrer until the magnesium chloride and the aluminum chloride are completely dissolved to obtain a mixed solution, wherein the concentrations of the magnesium chloride and the aluminum chloride in the mixed solution are 285mg/L and 133mg/L respectively. Weighing sodium hydroxide, dissolving the sodium hydroxide in water, and dropwise adding 6g/L sodium hydroxide solution into a mixed solution of magnesium salt and aluminum salt to obtain a slurry-like substance. Centrifuging the slurry-like substance at 5000-10000 rpm, and washing with pure water for three times. After the washing, hydrothermal treatment (105 ℃ C., 240 minutes) was carried out. And (4) freeze-drying the sample after the hydrothermal treatment, grinding the sample into powder, and sieving, sealing and storing the composite material.
(2) The potassium fluoride is dissolved in Nanjing tap water, the pH of the Nanjing tap water is 7.6, and the types and concentrations of anions are shown in Table 1. Preparing fluoride ion solutions with initial concentrations of 2.5, 5.0, 10.0 and 15.0mg/L, adding hydrochloric acid to adjust the pH of the fluorine-containing tap water to be below 6, adding 50mg/L of layered double hydroxide, quickly stirring for 2 minutes, slowly stirring for 15 minutes, flocculating and settling for 15 minutes, measuring the concentration of fluoride ions in the supernatant by using a fluoride ion selective electrode, and removing the fluoride ions as shown in FIG. 7. The removal rates of fluorine ions were 42%, 44%, 35% and 40%, respectively.
Comparative example B
This comparative example shows the removal of fluoride ion adsorption by zirconium salt alone, potassium fluoride was dissolved in Nanjing tap water having a pH of 7.6, and the anion species and concentrations are shown in Table 1.
Preparing fluoride ion solutions with initial concentrations of 2.5, 5.0, 10.0 and 15.0mg/L, adding hydrochloric acid to adjust the pH value of fluorine-containing tap water to be below 6, respectively adding zirconium chloride into the fluoride ion solutions with the addition concentration of 50mg/L, quickly stirring for 2 minutes, then slowly stirring for 15 minutes, flocculating and settling for 15 minutes, then measuring the concentration of fluoride ions in the supernatant by using a fluoride ion selective electrode, and removing results are shown in figure 8. The removal rates of the fluorine ions are 58%, 60%, 54% and 65%, respectively.
As can be seen from the comparison results of the comparative examples A and B and the examples 2-5, in the process of removing fluorine ions in a water body, the synergistic effect is exerted among the components in the composite material structure, and the specific removal of the fluorine ions is greatly enhanced.
Claims (10)
1. The composite material for deeply removing the fluorine ions in the wastewater is characterized in that: the composite material is a layered composite metal hydroxide which is prepared by a hydrothermal method and at least contains 3 metal hydroxides, and the layered composite metal hydroxide contains zirconium hydroxide.
2. The composite material for deeply removing fluorine ions in wastewater according to claim 1, wherein: the layered composite metal hydroxide contains zirconium hydroxide and aluminum hydroxide.
3. The composite material for deeply removing fluorine ions in wastewater according to claim 2, wherein: the layered composite metal hydroxide contains zirconium hydroxide, magnesium hydroxide and aluminum hydroxide.
4. The method for preparing the composite material for deeply removing the fluorine ions in the wastewater according to any one of claims 1 to 3, which is characterized in that: the method comprises the following steps:
1) preparing a mixed solution containing at least 3 metal ions, wherein the mixed solution contains zirconium ions;
2) dropwise adding a sodium hydroxide solution into the mixed solution to obtain a slurry-like substance;
3) centrifuging the slurry-like substance, washing with pure water, and centrifuging again to obtain a solid substance;
4) carrying out hydrothermal treatment, freeze drying, grinding into powder and sieving on the solid obtained in the step 3) to obtain the composite material.
5. The method for preparing the composite material for deeply removing the fluorine ions in the wastewater according to claim 4, wherein the method comprises the following steps: the preparation process of the step 1) is as follows: mixing magnesium salt, aluminum salt and zirconium salt to obtain a mixture, and adding water to dissolve the mixture to obtain a mixed solution; the added mass of the zirconium salt is not less than 5 percent of the total mass of the mixture.
6. The method for preparing the composite material for deeply removing the fluorine ions in the wastewater according to claim 5, wherein the method comprises the following steps: the amount of the sodium hydroxide is not less than 3 times of the total amount of magnesium, aluminum and zirconium.
7. The method for preparing the composite material for deeply removing the fluorine ions in the wastewater according to claim 5, wherein the method comprises the following steps: the centrifugation speed in the step 3) is 5000-10000 rpm, and/or the temperature of hydrothermal treatment in the step 4) is not lower than 60 ℃, and the treatment time is not less than 60 minutes.
8. The application method of the composite material for deeply removing the fluorine ions in the wastewater as claimed in any one of claims 1 to 3, is characterized in that: and adding the composite material into fluorine-containing wastewater to remove fluorine ions in the wastewater.
9. The application method for deeply removing the fluorine ions in the wastewater according to claim 8, is characterized in that: the concentration of the composite material in the wastewater is not lower than 25 mg/L.
10. The application method for deeply removing the fluorine ions in the wastewater according to claim 9, is characterized in that: the pH value of the wastewater is less than or equal to 6.
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| CN114873682A (en) * | 2022-06-10 | 2022-08-09 | 中关村至臻环保股份有限公司 | Low-cost water treatment agent for removing sulfate radicals and fluoride ions in mine water and preparation method thereof |
| CN114873682B (en) * | 2022-06-10 | 2023-09-05 | 中关村至臻环保股份有限公司 | Low-cost water treatment agent for removing sulfate radical and fluoride ions in mine water and preparation method thereof |
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