CN113816480B - Medicament and method for removing fluorine from mixed solution containing sulfate radical and fluorine ions - Google Patents
Medicament and method for removing fluorine from mixed solution containing sulfate radical and fluorine ions Download PDFInfo
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- CN113816480B CN113816480B CN202111175237.XA CN202111175237A CN113816480B CN 113816480 B CN113816480 B CN 113816480B CN 202111175237 A CN202111175237 A CN 202111175237A CN 113816480 B CN113816480 B CN 113816480B
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- fluorine
- mixed solution
- defluorination
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- fluoride
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- 239000011737 fluorine Substances 0.000 title claims abstract description 82
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 82
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011259 mixed solution Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 39
- -1 fluorine ions Chemical class 0.000 title claims abstract description 32
- 239000003814 drug Substances 0.000 title claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 22
- 239000011258 core-shell material Substances 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000306 component Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 3
- DGCPSAFMAXHHDM-UHFFFAOYSA-N sulfuric acid;hydrofluoride Chemical compound F.OS(O)(=O)=O DGCPSAFMAXHHDM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000008358 core component Substances 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 19
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 13
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004255 ion exchange chromatography Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001672 fluorine mineral Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UTWHRPIUNFLOBE-UHFFFAOYSA-H neodymium(3+);tricarbonate Chemical compound [Nd+3].[Nd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UTWHRPIUNFLOBE-UHFFFAOYSA-H 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The application particularly relates to a reagent and a method for removing fluorine from a mixed solution containing sulfate radicals and fluorine ions, which belong to the technical field of wastewater treatment, wherein the reagent comprises: the defluorinating agent and the catalyst are in a ratio of 0.01-0.4 by mass: 0.001-0.003; by utilizing the strong defluorination performance of the defluorination agent, under the action of a catalytic medium, the fluorine ion selectivity in the mixed solution and the defluorination agent are combined into fluorine-containing precipitates, and sulfate radicals in the solution do not participate in the reaction, so that the difficult problem of removing the fluorine ions in the sulfate radical-containing solution is solved, and the high-value utilization of fluorine resources in the wastewater is realized; the technology has the characteristics of simple process flow, low investment cost, easy industrialized stable disposal, zero emission of waste and the like.
Description
Technical Field
The application belongs to the technical field of wastewater treatment, and particularly relates to a reagent and a method for removing fluorine from a mixed solution containing sulfate radicals and fluorine ions.
Background
In many industrial processes, fluorine-containing wastewater is inevitably produced due to fluorine-containing raw materials or fluorine-containing substances added to the process. Such industries include the exploitation of fluorine minerals, synthesis of fluorides, smelting of rare earth metals and nonferrous metals, aluminum electrorefining, electroplating, coke, thermal power generation, glass, fluorosilicates, pesticides, cement, tile, acid cleaning of stainless steel, fertilizers, fluorochlorohydrocarbons, ceramics, washing of silicon-based electrical parts, petrochemical industry and other conventional industries; modern industries such as organic synthesis chemical industry, electronic integrated circuit industry, atomic energy industry and the like.
Fluorine in the fluorine-containing wastewater exists in the forms of sodium fluoride, hydrofluoric acid and other fluoride salts, and the fluorine content in various wastewater is different. For wastewater with higher fluorine concentration, the fluorine concentration of the effluent can be lower than 10mg/L after being treated by combining a plurality of methods, namely the emission standard of industrial wastewater. And the fluorine content is lower than 1.0mg/L, namely the standard of drinking water, and the fluorine content is required to be subjected to multistage adsorption treatment of the adsorbent. The practical industrial fluorine-containing wastewater often contains various pollutants, so that the treatment difficulty is increased, and particularly under the coexistence of fluoride ions and sulfate radicals in the solution, if the removal of fluorine is realized under the condition of retaining the sulfate radicals, the wastewater production enterprises are always plagued. Along with the rapid development of industry, the discharge amount of the fluorine-containing wastewater in China is inevitably increased year by year, and the fluorine-containing wastewater treatment and fluorine recycling recovery have important significance.
In recent years, along with the importance of the nation on the ecological environment, water treatment scientific researchers have developed a lot of productive work on the technology of removing fluorine in wastewater, and Chinese patent application CN111268830A discloses a system and a process for deeply treating and recycling fluorine-containing wastewater in the electronic industry, and the purposes of deeply treating and recycling fluorine-containing wastewater in the electronic industry are realized by adopting the processes of RO concentration, two-stage mixing, adding a fluorine removing agent and fluorine removing resin and combining. The process adopts multistage process treatment, has higher investment and operation cost, and in addition, the byproduct fluorine-containing resin belongs to hazardous waste and is required to be strictly treated according to related requirements. The Chinese patent application CN111634936A discloses a method for producing praseodymium and neodymium fluoride by utilizing fluorine-containing wastewater, which aims at the fluorine-containing wastewater produced in bastnaesite wet smelting, and the pH is adjusted, and the praseodymium and neodymium carbonate is added to precipitate fluorine, so that the problem of high cost of producing the praseodymium and neodymium fluoride can be solved, and the recovery of fluorine resources in the fluorine-containing wastewater is realized. The patent is only applicable to fluorine-containing wastewater generated in the process of generating bastnaesite in wet smelting, and has certain limitations. Chinese patent application CN1351968A discloses a method for treating metal processing integrated wastewater. The method for treating the high-fluorine-content high-suspended-matter acidic wastewater in the phosphate fertilizer production process is suitable for treating the solid-content suspended-matter high-fluorine-content acidic wastewater. The method uses calcium carbonate as main defluorinating agent and calcium oxide as auxiliary defluorinating agent, and returns part of solid sediment to be used as gathering seed crystal. The method has the advantages of wide medicament source, low price, short water treatment time, simple process and low water treatment cost.
In summary, the various methods of the prior art are essentially all based on Ca 2+ As a main reactant for removing fluorine, by Ca 2+ And F is equal to - Reaction to give water-insoluble CaF 2 Thereby achieving the purpose of removing most of fluorine in the wastewater. However, the above methods are difficult to be effectively applied to F in sulfate-containing wastewater - Because the formation of calcium sulfate interferes with the production efficiency and precipitation performance of calcium fluoride. Therefore, how to develop a method for removing fluorine from mixed liquor containing sulfate radical and fluorine ions becomes a key technical problem to be overcome by fluorine-containing wastewater treatment workers.
Disclosure of Invention
The application aims to provide a reagent and a method for removing fluorine from a mixed solution containing sulfate radicals and fluorine ions, so as to solve the problem that calcium ions influence the defluorination of the mixed solution at present.
The embodiment of the application provides a medicament for removing fluorine from a mixed solution containing sulfate radicals and fluorine ions, which comprises the following components: the defluorinating agent and the catalyst are in a ratio of 0.01-0.4 by mass: 0.001-0.003.
Optionally, the defluorinating agent has a core-shell structure, wherein the core component of the core-shell structure comprises at least one of nanoscale magnesium oxide, nanoscale magnesium hydroxide and magnesium sulfate, and the shell component of the core-shell structure comprises at least one of elemental silicon, scandium oxide and boric acid monomers.
Optionally, the granularity of the defluorinating agent is less than or equal to 0.15mm.
Optionally, the catalyst comprises at least one of titanium dioxide, manganese oxide and vanadium oxalate.
Based on the same inventive concept, the embodiment of the application also provides a method for removing fluorine from a mixed solution containing sulfate and fluorine ions, which comprises the following steps:
regulating the pH value of the mixed solution containing sulfate radicals and fluoride ions to obtain a pretreatment solution;
adding a reagent into the pretreatment solution, stirring and defluorinating to obtain defluorinated slurry;
carrying out solid-liquid separation on the defluorinated slurry to obtain a fluorine-containing precipitate;
wherein the medicament comprises: the defluorinating agent and the catalyst are in a ratio of 0.01-0.4 by mass: 0.001-0.003.
Optionally, the ratio of the pretreatment solution, the defluorinating agent and the catalyst is 1:0.01-0.4:0.001-0.003.
Optionally, the pH of the pretreatment solution is 5-8.
Optionally, the temperature of the mixed solution for stirring and defluorination is 15-80 ℃, and the stirring and defluorination time is 10-100 min.
Alternatively, the solid-liquid separation apparatus comprises a vacuum belt filter or centrifuge.
Optionally, in the fluorine-containing precipitate, the purity of fluoride is > 96%.
One or more technical solutions in the embodiments of the present application at least have the following technical effects or advantages:
the embodiment of the application provides a medicament for removing fluorine from a mixed solution containing sulfate radicals and fluorine ions, which comprises the following components: the defluorinating agent and the catalyst are in a ratio of 0.01-0.4 by mass: 0.001-0.003; by utilizing the strong defluorination performance of the defluorination agent, under the action of a catalytic medium, the fluorine ion selectivity in the mixed solution and the defluorination agent are combined into fluorine-containing precipitates, and sulfate radicals in the solution do not participate in the reaction, so that the difficult problem of removing the fluorine ions in the sulfate radical-containing solution is solved, and the high-value utilization of fluorine resources in the wastewater is realized; the technology has the characteristics of simple process flow, low investment cost, easy industrialized stable disposal, zero emission of waste and the like.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of a method provided by an embodiment of the present application.
Detailed Description
The advantages and various effects of the present application will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the application, not to limit the application.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, 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 application belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
The technical scheme of the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
according to an exemplary embodiment of the present application, there is provided a method for removing fluorine from a sulfate-and fluoride-containing mixed liquor, the method comprising:
s1, regulating the pH value of a mixed solution containing sulfate radicals and fluoride ions to obtain a pretreatment solution;
as an alternative embodiment, the pH of the pretreatment solution is in the range of 5 to 8.
The pH value of the pretreatment solution is controlled to be 5-8, and if the pH value is lower than 5 or higher than 8, the fluorine removal efficiency is reduced, and when the pH value of the solution is higher than 8, the purity of the defluorinated product is affected.
S2, adding the agent into the pretreatment solution, and stirring for defluorination to obtain defluorination slurry; the medicament comprises: the defluorinating agent and the catalyst are in a ratio of 0.01-0.4 by mass: 0.001-0.003.
The mass ratio of the mixed solution containing sulfate radical and fluoride ion to the defluorinating agent to the catalyst is controlled to be 1: (0.01-0.4): the reason for (0.001-0.003) is that: in the proportion range, the proceeding degree of defluorination reaction can be ensured, the high-efficiency precipitation of fluoride ions in the solution is realized, the purity of magnesium fluoride of a defluorination product is ensured to be controlled to be more than 96%, if the defluorination agent is added too little, the defluorination element is not easy to remove from the mixed solution, and if the defluorination agent is added too much, the cost control is not easy, and the purity of magnesium fluoride of a final product is also affected; if the catalyst is added too little, the defluorination time is long and the efficiency is low, and if the catalyst is added too much, the cost control is not facilitated, and excessive impurities are introduced.
As an alternative embodiment, the defluorinating agent has a core-shell structure, specifically, the core thereof comprises: one or more of nano-scale magnesium oxide, nano-scale magnesium hydroxide and magnesium sulfate, and the shell layer comprises one or more of simple substance silicon, scandium oxide and boric acid monomers.
As an alternative embodiment, the catalyst is one or more of titanium dioxide, manganese trioxide, vanadium oxalate.
As an alternative embodiment, the temperature of the mixed solution for stirring and defluorination is 15-80 ℃, and the stirring and defluorination time is 10-100 min.
Controlling the temperature of the mixed solution for stirring and defluorination to be 15-80 ℃, if the reaction temperature is less than 15 ℃, the magnesium fluoride crystal nucleus is limited in production and defluorination reaction dynamics are limited, the improvement of defluorination efficiency and the subsequent liquid-solid separation are unfavorable, and if the reaction temperature is more than 60 ℃, the steam amount is large and the energy consumption is high. The stirring defluorination time is controlled to be 10-100 min, if the reaction time is less than 10min, the reaction is insufficient, the fluorine removal rate is low, and if the reaction time is more than 60min, the treatment capacity is affected.
S3, carrying out solid-liquid separation on the defluorinated slurry to obtain fluorine-containing precipitate;
as an alternative embodiment, the liquid-solid separation may be centrifugal separation or vacuum belt filtration, and the apparatus used may be a vacuum belt filter or a centrifuge.
The purity of fluoride in the finally obtained fluorine-containing precipitate is more than 96 percent. Can be directly sold to the outside or used as fluxing agent for smelting magnesium, additive for electrolytic aluminum and coating of lenses and filters in optical instruments.
The agent and method for removing fluorine from a sulfate-and fluoride-containing ion-containing mixed solution of the present application will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
Weighing 500ml of mixed solution containing sulfate radicals and fluoride ions, and carrying out pretreatment on the mixed solution to adjust the pH value to 6.8; then respectively adding the weighed defluorinating agent and the catalyst into the pretreated mixed solution, and rapidly stirring; wherein the amount of defluorination and the amount of catalyst are respectively 0.12 times and 0.002 times of the mass of the mixed solution; heating and stirring for 45min in a water bath kettle at 30 ℃ to obtain defluorinated slurry; the defluorinated slurry is subjected to liquid-solid separation in a centrifuge tube, the concentration of fluoride ions in the centrifugate is analyzed to be 7.6mg/L by adopting an ion chromatography method, and a solid phase of the liquid-solid separation is dried to obtain magnesium fluoride powder with the purity of 97.2 percent, which can be directly sold to the outside or used as a fluxing agent for smelting magnesium metal, an additive for electrolytic aluminum and a coating of a lens and an optical filter in an optical instrument, thereby realizing the removal and recycling of fluorine in a sulfate-containing solution.
Example 2
1000ml of mixed solution containing sulfate radical and fluoride ion is weighed, and is pretreated to adjust the pH value to 8; then respectively adding the weighed defluorinating agent and the catalyst into the pretreated mixed solution, and rapidly stirring; wherein the amount of defluorination and the amount of catalyst are respectively 0.01 times and 0.003 times of the mass of the mixed solution; heating and stirring for 100min in a water bath kettle at 15 ℃ to obtain defluorinated slurry; the defluorinated slurry is subjected to liquid-solid separation in a centrifuge tube, the concentration of fluorine ions in the centrifugate is analyzed to be 45.6mg/L by adopting an ion chromatography method, and a solid phase of the liquid-solid separation is dried to obtain magnesium fluoride powder with the purity of 94.2 percent, which can be directly sold to the outside or used as a fluxing agent for smelting magnesium metal, an additive for electrolytic aluminum and a coating of a lens and an optical filter in an optical instrument, thereby realizing the removal and recycling of fluorine in a sulfate-containing solution.
Example 3
2000ml of mixed solution containing sulfate radical and fluoride ion is weighed, and is pretreated to adjust the pH value to 5; then respectively adding the weighed defluorinating agent and the catalyst into the pretreated mixed solution, and rapidly stirring; wherein the amount of defluorination and the amount of catalyst are respectively 0.4 times and 0.001 times of the mass of the mixed solution; heating and stirring for 10min in a water bath kettle at 80 ℃ to obtain defluorinated slurry; the defluorinated slurry is subjected to liquid-solid separation in a centrifuge tube, the concentration of fluorine ions in the centrifugate is analyzed to be 21.0mg/L by adopting an ion chromatography method, and a solid phase of the liquid-solid separation is dried to obtain magnesium fluoride powder with the purity of 92.1 percent, so that the magnesium fluoride powder has high impurity content and can be considered as a fluxing agent for smelting magnesium metal and an additive for electrolytic aluminum, and the removal and recycling of fluorine in a sulfate-containing solution are realized.
Example 4
1000ml of mixed solution containing sulfate radical and fluoride ion is weighed, and is pretreated to adjust the pH value to 7.0; then respectively adding the weighed defluorinating agent and the catalyst into the pretreated mixed solution, and rapidly stirring; wherein the amount of defluorination and the amount of catalyst are respectively 0.18 times and 0.002 times of the mass of the mixed solution; heating and stirring for 60min in a water bath kettle at 55 ℃ to obtain defluorinated slurry; the defluorinated slurry is subjected to liquid-solid separation in a centrifuge tube, the concentration of fluorine ions in the centrifugate is analyzed by adopting an ion chromatography method to be 8.6mg/L, and a solid phase of the liquid-solid separation is dried to obtain magnesium fluoride powder with the purity of 97.4 percent, which can be directly sold to the outside or used as a fluxing agent for smelting magnesium metal, an additive for electrolytic aluminum and a coating of a lens and an optical filter in an optical instrument, thereby realizing the removal and recycling of fluorine in a sulfate-containing solution.
Example 5
200ml of mixed solution containing sulfate radicals and fluoride ions is weighed, and is pretreated to adjust the pH value to 6.2; then respectively adding the weighed defluorinating agent and the catalyst into the pretreated mixed solution, and rapidly stirring; wherein the amount of defluorination and the amount of catalyst are respectively 0.24 times and 0.002 times of the mass of the mixed solution; heating and stirring in a water bath kettle at 70 ℃ for 70min to obtain defluorinated slurry; the defluorinated slurry is subjected to liquid-solid separation in a centrifuge tube, the concentration of fluorine ions in the centrifugate is analyzed to be 11.6mg/L by adopting an ion chromatography method, and a solid phase of the liquid-solid separation is dried to obtain magnesium fluoride powder with the purity of 96.2 percent, which can be directly sold to the outside or used as a fluxing agent for smelting magnesium metal, an additive for electrolytic aluminum and a coating of a lens and an optical filter in an optical instrument, thereby realizing the removal and recycling of fluorine in a sulfate-containing solution.
Comparative example 1
400ml of mixed solution containing sulfate radical and fluoride ion is weighed, and the pH value is adjusted to 9.0 by pretreatment; then respectively adding the weighed defluorinating agent and the catalyst into the pretreated mixed solution, and rapidly stirring; wherein the amount of defluorination and the amount of catalyst are respectively 0.15 times and 0.001 times of the mass of the mixed solution; heating and stirring for 60min in a water bath kettle at 65 ℃ to obtain defluorinated slurry; and (3) carrying out liquid-solid separation in the defluorinated slurry centrifuge tube, analyzing the concentration of fluoride ions in the centrifugate by adopting an ion chromatography method to be 83.9mg/L, and drying a solid phase of the liquid-solid separation to obtain the magnesium fluoride powder with the purity of 90.2%. The fluoride removal rate and the purity of the final defluorinated product are both inferior to those of the examples.
Comparative example 2
Weighing 500ml of mixed solution containing sulfate radicals and fluoride ions, and carrying out pretreatment on the mixed solution to adjust the pH value to 6.9; then respectively adding the weighed defluorinating agent and the catalyst into the pretreated mixed solution, and rapidly stirring; wherein the amount of defluorination and the amount of catalyst are respectively 0.002 times and 0.001 times of the mass of the mixed solution; heating and stirring for 30min in a water bath kettle at 75 ℃ to obtain defluorinated slurry; and (3) carrying out liquid-solid separation in a defluorinated slurry centrifuge tube, analyzing the concentration of fluorine ions in the centrifugate by adopting an ion chromatography method to be 1586mg/L, and drying a solid phase subjected to liquid-solid separation to obtain magnesium fluoride powder with the purity of 96.6%. Because the addition amount of the defluorinating agent is small, the removal of the fluorine ions in the solution is incomplete, and the fluorine concentration of the effluent is far higher than the emission standard of industrial wastewater.
Comparative example 3
2000ml of mixed solution containing sulfate radical and fluoride ion is weighed, and is pretreated to adjust the pH value to 7.5; then respectively adding the weighed defluorinating agent and the catalyst into the pretreated mixed solution, and rapidly stirring; wherein the amount of defluorination and the amount of catalyst are respectively 0.26 times and 0.0005 times of the mass of the mixed solution; heating and stirring for 100min in a water bath kettle at 75 ℃ to obtain defluorinated slurry; and (3) carrying out liquid-solid separation in the defluorinated slurry centrifuge tube, analyzing the concentration of fluorine ions in the centrifugate by adopting an ion chromatography method to be 360mg/L, and drying a solid phase subjected to liquid-solid separation to obtain magnesium fluoride powder with the purity of 96.9%. Because the catalyst addition amount is less, the defluorination reaction rate is lower, the reaction is incomplete within 100min, and the fluorine concentration of the effluent is far higher than the emission standard of industrial wastewater.
One or more technical solutions in the embodiments of the present application at least have the following technical effects or advantages:
(1) The method provided by the embodiment of the application utilizes the strong defluorination performance of the defluorination agent, under the action of the catalytic medium, the fluorine ion selectivity in the mixed solution and the defluorination agent are combined into fluorine-containing precipitate, sulfate radical in the solution does not participate in the reaction, so that the difficult problem of removing fluorine ions in the sulfate radical-containing solution is solved, and the high-value utilization of fluorine resources in the wastewater is realized; the technology has the characteristics of simple process flow, low investment cost, easy industrialized stable treatment, zero emission of waste and the like;
(2) The method provided by the embodiment of the application adopts a one-step precipitation method to selectively remove the fluoride ions in the sulfate radical-containing solution, thereby avoiding the loss of sulfate radicals and ensuring the purity of defluorinated products;
(3) Compared with the traditional defluorinated product calcium fluoride, the magnesium fluoride prepared by the method provided by the embodiment of the application has higher added value, larger market demand and wider technical popularization and application prospect.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (1)
1. A method for removing fluorine from a sulfate-and fluoride-containing mixed liquor, the method comprising: regulating the pH value of the mixed solution containing sulfate radicals and fluoride ions to 5-8 to obtain a pretreatment solution;
adding a reagent into the pretreatment solution, stirring and defluorinating to obtain defluorinated slurry;
carrying out solid-liquid separation on the defluorinated slurry to obtain a fluorine-containing precipitate;
wherein the medicament comprises: the defluorinating agent and the catalyst are in a ratio of 0.01-0.4 by mass: 0.001-0.003, wherein the defluorinating agent has a core-shell structure, the core component of the core-shell structure comprises at least one of nano-scale magnesium oxide, nano-scale magnesium hydroxide and magnesium sulfate, the shell component of the core-shell structure comprises at least one of simple substance silicon, scandium oxide and boric acid monomer, and the catalyst comprises at least one of titanium dioxide, manganese sesquioxide and vanadium oxalate; the ratio of the pretreatment solution, the defluorinating agent and the catalyst is 1 by mass: 0.01-0.4:0.001-0.003;
the granularity of the defluorinating agent is less than or equal to 0.15mm;
the temperature of the mixed solution for stirring and defluorination is 15-80 ℃, and the stirring and defluorination time is 10-100 min;
the equipment for solid-liquid separation comprises a vacuum belt filter or a centrifuge;
in the fluorine-containing precipitate, the purity of fluoride is more than 96 percent.
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