WO2003066533A1 - Procede de recuperation d'un agent emulsifiant fluorochimique - Google Patents

Procede de recuperation d'un agent emulsifiant fluorochimique Download PDF

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Publication number
WO2003066533A1
WO2003066533A1 PCT/JP2003/000659 JP0300659W WO03066533A1 WO 2003066533 A1 WO2003066533 A1 WO 2003066533A1 JP 0300659 W JP0300659 W JP 0300659W WO 03066533 A1 WO03066533 A1 WO 03066533A1
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Prior art keywords
emulsifier
layered double
double hydroxide
fluorinated
fluorine
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PCT/JP2003/000659
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English (en)
Japanese (ja)
Inventor
Koichi Yanase
Masataka Eda
Hiroki Kamiya
Kota Omori
Takeshi Kamiya
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Jemco Inc.
Asahi Glass Company, Limited
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Application filed by Jemco Inc., Asahi Glass Company, Limited filed Critical Jemco Inc.
Priority to AU2003203383A priority Critical patent/AU2003203383A1/en
Publication of WO2003066533A1 publication Critical patent/WO2003066533A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • 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
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/301—Detergents, surfactants
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/38—Polymers

Definitions

  • the present invention relates to a method for recovering a fluorinated emulsifier using a layered double hydroxide.
  • IER anion exchange resin
  • Patent Document 2 (US 3882153) describes a method in which a dilute emulsifier aqueous solution is brought into contact with a weakly basic IER within a pH range of 0 to 7 to adsorb the emulsifier and desorb it with aqueous ammonia. .
  • Patent Document 3 discloses that a nonionic or cationic surfactant is added to coagulated waste water of a fluorine-containing polymer, and fine particles of polytetrafluoroethylene (hereinafter referred to as PTFE) in the coagulated waste water. Methods are described to stabilize and prevent clogging of the packed tower of the IER.
  • PTFE polytetrafluoroethylene
  • Patent Document 4 Japanese Patent Application Laid-Open No. 55-120630
  • Patent Document 5 US Pat. No. 4,369,266
  • Patent Document 6 DE 2908001
  • Patent Document 2 Japanese Patent Application Laid-Open No. 55-104651
  • Patent Document 8 Japanese Patent Application Laid-Open No. 55-104651
  • Patent Document 8 DE 2903981
  • Patent Document 9 discloses a coagulated drainage of a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (hereinafter referred to as PFA). Then, lime water is added in advance to adjust the pH to 6 to 7.5, and a metal salt such as aluminum chloride or iron chloride is added to coagulate unagglomerated PFA. A method is described in which after separation and removal, the pH of the obtained wastewater is adjusted to 7 or less with sulfuric acid, and the fluorinated emulsifier is adsorbed and recovered using a strongly basic IER.
  • PFA tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2000-61231 discloses a method of desorbing a fluorine-containing emulsifier adsorbed on an ion-exchange resin using a mixed solution of water, an alkali and an organic solvent. Is described.
  • Non-Patent Document 1 (Chemical Proceedings of the 76th Annual Meeting of the Chemical Society of Japan, Published on March 15, 2001, p. 600) and Non-Patent Document 2 (Chemical Society of Japan No. 80 Proceedings of the Annual Meeting of the Autumn Meeting, published on September 7, 2001, p. 41), using perfluorooctanoic acid and its ammonium salt using layered double hydroxides of aluminum and zinc. Insertion and fixation techniques have been reported.
  • Non-patent Documents 1 and 2 only shows insertion fixing with an aqueous solution in which only perfluorooctanoic acid and its ammonium salt are dissolved.
  • the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for easily recovering a fluorine-containing emulsifier from a coagulated drainage of a fluorine-containing polymer containing a fluorine-containing emulsifier using a layered double hydroxide. I have. Disclosure of the invention
  • the present invention provides a mixed aqueous solution containing a divalent metal ion and a trivalent metal ion, a fluorinated emulsifier, and a content of a suspended solid and a substance that can be a suspended solid.
  • the wastewater after polymerization of the fluorine-containing polymer of 1% by mass or less is maintained at a pH at which a layered double hydroxide of the divalent metal and the trivalent metal is formed.
  • a method for recovering a fluorinated emulsifier, comprising extracting the fluorinated emulsifier is provided.
  • the present invention provides a method of adding a mixed aqueous solution containing a divalent metal ion and a trivalent metal ion to an aqueous solution maintained at pH at which a layered double hydroxide of the divalent metal and the trivalent metal is formed.
  • a layered double hydroxide is generated in advance and added to wastewater after polymerization of a fluorine-containing polymer containing a fluorine-containing emulsifier and containing 1% by mass or less of a suspended solid and a substance that can become a suspended solid.
  • a layered double hydroxide containing a fluorinated emulsifier between layers dissolve the layered double hydroxide separated from the wastewater in a mineral acid, and use the fluorinated hydrocarbon from the dissolved solution.
  • a method for recovering a fluorine-containing emulsifier comprising extracting the fluorine-containing emulsifier.
  • the present invention provides a method in which a mixed aqueous solution containing a divalent metal ion and a trivalent metal ion is added to the aqueous solution maintained at ⁇ at which the layered double hydroxide of the divalent metal and the trivalent metal is formed.
  • a layered double hydroxide in which the anion contained therein has been desorbed is generated, and this is a material containing a fluorine emulsifier, which can be a suspended solid and a substance that can be a suspended solid.
  • a method for recovering a fluorinated emulsifier comprising: dissolving fluorinated emulsifier in a mineral acid; and extracting the fluorinated emulsifier from the solution using a fluorinated hydrocarbon.
  • the divalent metal ion is preferably one or two selected from a magnesium ion and a zinc ion, and the trivalent metal ion is preferably an aluminum ion.
  • the mineral acid is preferably at least one selected from the group consisting of hydrochloric acid, nitric acid and sulfuric acid.
  • the fluoropolymer includes polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene / propylene copolymer, tetrafluoroethylene-propylene / vinylidene fluoride copolymer, and tetrafluoroethylene.
  • Chemical styrene ⁇ hexafluoride Kapuguchipi alkylene copolymer, tetrafluoroethylene modified styrene / CF 2 CFO (CF 3 ⁇ 4 ) 2 CF 3 copolymer, ⁇ And one or more selected from polyvinylidene fluoride.
  • the fluorine-containing emulsifier is ammonium perfluorooctanoate.
  • the fluorinated emulsifier salts such as perfluoroalkanoic acid, ⁇ -hydroperfluoroalkanoic acid, ⁇ -chloroperfluoroalkanoic acid, and perfluoroalkanesulfonic acid having 5 to 13 carbon atoms are used. It is preferable that they have a linear structure or a branched structure, or a mixture thereof. Further, the molecule may contain an etheric oxygen atom. When the number of carbon atoms is in this range, the effect as an emulsifier is excellent.
  • an alkali metal salt such as a lithium salt, a sodium salt, and a potassium salt or an ammonium salt is preferable, an ammonium salt or a sodium salt is more preferable, and an ammonium salt is most preferable.
  • the acid include perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, and perfluoropentanoic acid.
  • ammonium salts include 'acid ammonium, Ammonium perfluorohexanoate, ammonium perfluoroheptanoate, ammonium perfluorooctanoate (hereinafter referred to as APFO), ammonium perfluorononanoate, ammonium perfluorodecanoate, ammonium perfluorodecanoate, ⁇ -hydroperfluoroheptanoate ammonium, ⁇ -hydroperfluorooctanoate ammonium, ⁇ -hydroperfluorononanoate ammonium, ⁇ -cloperperfluoroheptanoate ammonium, ⁇ -clo Oral perfluorooctanoic acid ammonium, ⁇ -chloroperfluorononanoic acid ammonium, etc.
  • APFO ammonium perfluorononanoate
  • ammonium perfluorodecanoate ammonium perfluorodecano
  • ammonium perfluorohexane sulfonate ammonium perfluoroheptane sulfonate, ammonium perfluorooctane sulfonate, ammonium perfluorononane sulfonate, ammonium perfluorodecane sulfonate, and the like.
  • lithium salt examples include lithium perfluoropentanoate, lithium perfluorohexanoate, lithium perfluoroheptanoate, lithium perfluorooctanoate, lithium perfluorononanoate, and lithium perfluoronate.
  • CF 3 CF 2 CF 2 OCF (CF 3 ) COOL i CF 3 CF 2 CF 2 ⁇ CF (CF 3 ) CF 2 OCF (CF 3 ) COOL i, CF 3 CF 2 CF 20 (CF (CF 3 ) CF 2 0] 2 CF (CF 3 ) COOL i, CF 3 CF 2 CF 2 0 [CF (CF 3 ) CF 20 ] 3 CF (CF 3 ) COOL i, CF 3 CF 2 CF 2 CF 2 OCF ( CF 3 ) COOL i, etc.
  • Lithium perfluorohexane sulfonate Lithium, lithium perfluorooctanesulfonate,
  • sodium salt examples include sodium perfluoropentanoate, sodium perfluorohexanoate, sodium perfluorohepnoate, sodium perfluorooctanoate, sodium perfluorononanoate, sodium perfluorononate, sodium perfluorodenoate, Sodium perfluorododecanoate, Sodium hydroperfluoroheptanoate, Sodium hydroperfluorooctanoate, Sodium hydroperfluorononanoate, Sodium hydroperfluorononanoate, Sodium heptanoate, sodium ⁇ -cloper perfluorooctanoate, sodium ⁇ -cloper perfluorononanoate, etc.
  • CF 3 CF 2 CF 2 OCF (CF 3 ) COON a CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COON a, CF 3 CF 2 CF 2 0 [CF (CF 3 ) CF 2 0] 2 CF (CF 3 ) COON a, CF 3 CF 2 CF 2 0 [CF (CF 3 ) CF 20 ] 3 CF (CF 3 ) COON a, CF 3 CF 2 CF 2 CF 2 OCF (CF 3 ) COONa and the like, sodium acid, sodium perfluorooctanesulfonate, sodium perfluorononanesulfonate, sodium perfluorodecanesulfonate and the like.
  • potassium salt examples include potassium perfluoropentanoate, potassium perfluorohexanoate, potassium perfluoroheptanoate, potassium perfluorooctanoate, potassium perfluorononanoate, and perfluolonate.
  • potassium perfluoronate and potassium perfluorodecane sulfonate are preferable, and ammonium perfluoroheptanoate, APFO, ammonium perfluorononanoate or perfluonium Ammonium orolodecanoate is more preferred, and APFO is most preferred.
  • the effluent after polymerization of the fluorinated polymer is the effluent after separating the fluorinated polymer obtained by polymerizing at least one fluorinated monomer in an aqueous medium containing a fluorinated emulsifier.
  • coagulation wastewater of the fluoropolymer after emulsion polymerization is preferable, and coagulation wastewater from the process of producing a polymer of the fluoromonomer or a copolymer of the fluoromonomer and a monomer other than the fluoromonomer is particularly preferable. .
  • the coagulated waste water from the production step is obtained by emulsion polymerization or aqueous dispersion polymerization of a fluorinated monomer or a fluorinated monomer and a monomer other than the fluorinated monomer in an aqueous medium containing a fluorinated emulsifier.
  • This refers to waste water obtained by coagulating a fluoropolymer from the obtained aqueous dispersion of a fluoropolymer by salting out or the like and separating the fluoropolymer.
  • the wastewater contains not only the fluorinated emulsifier used in the polymerization of the fluorinated monomer but also an SS component such as a non-aggregated fluorinated polymer.
  • an SS component such as a non-aggregated fluorinated polymer.
  • VdF vinylene fluoride
  • HEP hexafluoropropylene
  • Monomers other than the fluorinated monomer include vinyl esters such as vinyl acetate, pinyl ethers such as ethyl vinyl ether, cyclohexyl vinyl ether, and hydroxybutyl vinyl ether; monomers having a cyclic structure such as norpolenene and norbonagen; Examples thereof include aryl ethers such as a lyl ether, ethylene (hereinafter, referred to as E), propylene (hereinafter, referred to as P), and olefins such as isobutylene. Monomers other than the fluorinated monomer may be used alone or in combination of two or more.
  • examples of the fluoropolymer include PTFE, TFE / P copolymer, TFEZPZVd F copolymer, TFE / HFP copolymer, PFA / PPVE copolymer, EZTFE copolymer, polyvinylidene fluoride and the like.
  • PTFE PTFE
  • TFEZP copolymer TFE / PZVdF copolymer
  • PFA / PPVE copolymer EZTFE copolymer
  • polyvinylidene fluoride and the like can be More preferably, it is PTFE, TFEZP copolymer, TFE / PZVdF copolymer or PFA / PPVE copolymer, most preferably PTFE.
  • a method of adding divalent and trivalent metal ions to the coagulated waste water of a fluorine-containing polymer (hereinafter referred to as a coprecipitation method), A method of adding a layered double hydroxide formed in a solution containing no emulsifier to the coagulated wastewater of a fluorine-containing polymer (hereinafter referred to as an ion exchange method); and a method of forming a layered double hydroxide formed in a solution containing no fluorine-containing emulsifier. It is possible to use a method in which the hydroxide is calcined and then added to the coagulated wastewater of the fluorine-containing polymer (hereinafter referred to as a reconstitution method).
  • potassium hydroxide and / or sodium hydroxide are added in advance to adjust the PH of the wastewater. Adjust to 6 or more and 9 or less when using aluminum ion and zinc ion, and 9 or more and 11 or less when using aluminum ion and magnesium ion. If the pH is out of the above range, In the method of adding a salt of aluminum and zinc or a salt of aluminum and magnesium to water, these metals form hydroxides individually and form aluminum hydroxide, zinc hydroxide, and magnesium hydroxide.
  • the concentration of the fluorinated emulsifier to be recovered is preferably 1 ppm (based on mass, the same applies hereinafter) or more and 10 mass% or less, more preferably 10 ppm or more and 1 mass% or less, particularly preferably 50 ppm or less.
  • the content is preferably at least 0.5% by mass.
  • concentration of the fluorinated emulsifier is 1 ppm or more, there is no problem that the efficiency of capturing the fluorinated emulsifier by the layered double hydroxide in the recovered liquid is reduced.
  • the concentration of the fluorine-containing emulsifier is higher than 10% by mass, a simpler and more efficient method such as precipitation of the fluorine-containing emulsifier by changing pH can be used.
  • Substances that can become suspended solids and suspended solids, such as unagglomerated fluoropolymer fine particles, contained in the flocculated wastewater are used to recover the fluorine-containing emulsifier and Although it does not adversely affect the recovery rate, it may hinder the regeneration of the fluorinated emulsifier from the generated layered double hydroxide, so remove it to 1% by mass or less before forming the layered double hydroxide. It is important to keep.
  • the SS component in the coagulated wastewater is more preferably removed to 0.3% by mass or less, particularly preferably to 0.05% by mass or less.
  • the substance that can become a suspended solid include a metal salt used for salting out and coagulation of a fluoropolymer and / or a substance that precipitates due to a change in pH of the coagulated wastewater.
  • salting out by adding a metal salt containing a polyvalent metal cation to coagulate the S S component is effective.
  • the metal salt include metal chlorides such as aluminum chloride, polyaluminum chloride, ferrous chloride, and ferric chloride.
  • Agglomerates generated by salting out should precipitate in the state containing APFO. Therefore, it is preferable to re-dissolve APFO from aggregates in water by adjusting the pH to 7 or more by adding sodium hydroxide and / or Z or a hydroxylating steam.
  • a common solid-liquid separation method can be used as a method for removing the SS component aggregates obtained by adding the above-mentioned metal chloride to the aggregated wastewater, particularly from filtration, decantation, centrifugation and thickener. It is more preferable to use one or more methods selected from the group consisting of: The filtration is also preferably performed under pressure. Further, it is preferable that the wastewater containing the aggregate is allowed to stand still, the aggregate is settled, and the supernatant is filtered to remove the aggregate. Thickeners or screw decanters are most preferable in terms of facility maintenance.
  • a trivalent metal (a metal that becomes a trivalent ion when ionized) and a divalent metal (a metal that becomes divalent ion when ionized) used to form the layered double hydroxide are used.
  • Metal has a range in which the pH of the ion of the trivalent metal forms a hydroxide overlaps with the range of the pH in which the ion of the divalent metal forms a hydroxide, or If the range of H is close, a layered double hydroxide can be formed.
  • Examples of the divalent metal include beryllium, cadmium, cobalt, chromium (II), copper (II), iron (II), magnesium, manganese (II), nickel, lead, platinum, palladium, zinc, tin, and calcium. And the like.
  • Examples of the trivalent metal include aluminum, bismuth, cerium, chromium (II), iron (III), gallium, indium, manganese (III), titanium, and thallium. In consideration of the effect on the environment and the availability, in the present invention, it is preferable to use one or two selected from magnesium and zinc as the divalent metal and to use aluminum as the trivalent metal. .
  • the preferable divalent metal and trivalent metal are used will be described.
  • the pH of the wastewater is 9 or more when the layered double hydroxide of aluminum and magnesium is used. Adjust to the following. Then, an aqueous solution in which the molar ratio of aluminum ion: magnesium ion is 1: 2 and the concentration of aluminum ion and magnesium ion is 0.0 lmo 1 ZL or more and 2 mo 1 ZL or less is added while stirring. I do.
  • Aluminum There is no problem with using any kind of raw material, but aluminum ion is preferably aluminum chloride, aluminum chloride hexahydrate, aluminum sulfate, or aluminum nitrate because of its availability. Aluminum chloride, aluminum chloride hexahydrate Japanese is more preferred.
  • magnesium chloride magnesium chloride hexahydrate, magnesium nitrate hexahydrate, magnesium nitrate, magnesium oxide, magnesium sulfate, magnesium sulfate heptahydrate, and magnesium carbonate
  • chloride Magnesium and magnesium chloride hexahydrate are preferred.
  • the pH of the wastewater is adjusted to 6 or more and 9 or less when the layered double hydroxide of aluminum and zinc is used as described above. Then, an aqueous solution in which the molar ratio of aluminum ion: zinc ion is 1: 2 and the concentration of aluminum ion and zinc ion is 0.0 lmo 1 / L or more and 2 mo 1 ZL or less is added with stirring.
  • Aluminum ion and zinc ion can be made of any raw material, but aluminum ion is preferably aluminum chloride, aluminum chloride hexahydrate, aluminum sulfate, or aluminum nitrate because of availability. More preferably, aluminum chloride and aluminum chloride hexahydrate are used.
  • As a raw material for zinc ions it is preferable to use zinc chloride, zinc nitrate hexahydrate, zinc oxide, zinc sulfate, and zinc sulfate heptahydrate, and zinc chloride is more preferable.
  • a mixed aqueous solution containing divalent and trivalent metal ions (hereinafter, referred to as a metal ion aqueous solution) is preferably used in an aqueous solution having a concentration of not less than 0.01 mO 17 and not more than 211101 ZL. If the metal ion concentration is lower than this, the amount of water increases when the required metal is added, and the total amount of the layered double hydroxide dissolved in the aqueous solution increases, which is not preferable.
  • the metal ion concentration is higher than this, since the metal ion aqueous solution is acidic, when forming the layered double hydroxide, a part of the aqueous solution is locally layered double hydroxide by adding the metal ion aqueous solution.
  • the metal ion is not effectively used for forming a layered double hydroxide.
  • a layered double hydroxide can be synthesized by adding a metal ion aqueous solution having an appropriate concentration range again.
  • the amount of the layered double hydroxide to be added to the coagulated waste water of the fluoropolymer is as follows: 03 00659
  • the trivalent ions in the double hydroxide are at least 1 mol times and at most 30 mol times with respect to the fluorinated emulsifier, and the divalent ions are at least 1 mol time and at most 60 mol times with respect to the fluorinated emulsifier. preferable.
  • the molar ratio of trivalent ions to divalent ions in the layered double hydroxide is 3
  • : 1: 1: 3 is preferable, and 1: 1 to 1: 3 is more preferable.
  • the amount of the calcined layered double hydroxide 1 mole or more the recovery rate of the fluorinated emulsifier is improved, and the amount of the layered double hydroxide to be added is within the above range. Since the ratio of the fluorinated emulsifier to the layered double hydroxide becomes too small, it is possible to eliminate the problem that the final regeneration efficiency of the fluorinated emulsifier is reduced. In addition, excessive use of the layered double hydroxide is not preferable from the viewpoint of increasing the load in the final wastewater treatment process due to the contained metal component.
  • the stirring method is not particularly limited, but is preferably a method that does not mechanically destroy the aggregate particles generated by the stirring.
  • a stirring blade of such a stirring device a stirring blade capable of uniformly mixing the entire wastewater at a low rotation speed is preferable, and one type selected from the group consisting of a full zone blade, a max blend blade, and an anchor blade is preferable.
  • G value during stirring at the stirring blade is preferably from 1 to 3 0 0 s-1, more preferably from 5 to 2 5 0 s 1,
  • the G value is a value derived by the following equation.
  • the firing of the layered double hydroxide is preferably performed at a temperature of at least 300 ° C. and less than 600 ° C., more preferably at least 400 and less than 500 ° C. At temperatures lower than this, the contained carbonate ions are not sufficiently desorbed, or it takes a long time for sufficient desorption. If the temperature is higher than this, the crystal structure of the layered double hydroxide collapses, which causes a reduction in the recovery efficiency of the fluorinated emulsifier.
  • the reaction is preferably carried out at a water temperature of 10 ° C. or more and 50 ° C. or less. If the water temperature is lower or higher than this, the recovery of the fluorinated emulsifier by the layered double hydroxide decreases. In particular, it is preferable to equip the reactor with a heating device because the recovery rate at a lower water temperature is significantly reduced.
  • a layered double hydroxide containing a fluorinated emulsifier between layers is generated in the coagulated wastewater.
  • the fluorinated emulsifier is separated from the coagulated wastewater. Can be recovered.
  • a well-known solid-liquid separation method can be used as appropriate, and in particular, at least one selected from the group consisting of filtration, decantation, centrifugation, and thickener It is more preferable to use the method described above.
  • the filtration is also preferably performed under pressure.
  • the fluorinated emulsifier recovered in the form of being encapsulated in the layered double hydroxide is, for example, redissolved the layered double hydroxide with hydrochloric acid and / or sulfuric acid and a strong acid such as Z or nitric acid. It can be regenerated by a method such as extraction from a liquid with a water-insoluble organic solvent.
  • Mineral acids used in the present invention include hydrochloric acid, sulfuric acid, and nitric acid.
  • hydrochloric acid is preferred.
  • Hydrochloric acid is an acid having a boiling point of 85 ° C, and hydrochloric acid mixed into the extract can be easily removed from the extract by a subsequent concentration operation.
  • the fluorinated hydrocarbon in the present invention those having 2 or 3 carbon atoms and containing one or more hydrogen atoms and one or more fluorine atoms are preferable.
  • the boiling point of the fluorinated hydrocarbon is preferably 5 to 120 ° C, more preferably 10 to 80 ° C. When it is in this range, the fluorinated hydrocarbon can be easily distilled and recovered, which is preferable.
  • C 3 HC 1 2 F 5 and C 3 H 3 F 1 or more to 5 selected from the group consisting of.
  • C 3 H 3 F 5 examples include CF 3 CH 2 CHF 2 , CF 3 CHFCH 2 F, and CHF 2 CH FCH F 2 , with CF 3 CH 2 CHF 2 being most preferred.
  • the fluorine-containing hydrocarbon and most preferably CF 3 CF 2 CHC 1 2, CC 1 F 2 CF 2 CHC 1 F and CF 3 CH 2 1 or more selected from the group consisting of CHF 2.
  • chlorinated hydrocarbons when chlorinated hydrocarbons are used for the extraction of fluorinated emulsifiers, it is necessary to treat chlorinated hydrocarbons that dissolve in the aqueous phase, whereas the solubility of fluorinated hydrocarbons in water is chlorinated hydrocarbons. Such a process is not necessary because it is lower.
  • conventionally used devices and equipment can be used for the above-mentioned extraction operation of the fluorinated emulsifier.
  • the extraction device include a batch extraction device, a cocurrent multiple extraction device, a countercurrent multistage extraction device, and a continuous countercurrent extraction device.
  • the extraction conditions were as follows: at a temperature lower than the boiling point of the solvent, a layered double hydroxide containing a fluorinated emulsifier was added between the layers.
  • the acid solution and the extraction solvent are mixed. Usually, 20 to 100% by mass, preferably 30 to 50% by mass of the extraction solvent is added to the acid solution.
  • the extraction rate of the fluorinated emulsifier is improved, but the throughput of the solvent in steps such as concentration is increased.
  • the extraction medium is dispersed in the acid solution by stirring, flowing, shaking, or the like.
  • the dispersion is performed so that the diameter of the droplets of the extraction medium is 0.1 mm or less, the extraction is completed in less than 10 minutes.
  • the extraction is completed, allow to stand to separate the aqueous and medium phases. Separation is required until the interface between the two phases is clear, but this is usually achieved in less than 10 minutes.
  • the concentration of APFO, perfluorooctanoic acid (hereinafter referred to as PFOA) or sodium perfluorooctanoate is determined by a high-performance liquid chromatography using a mixed solution of methanol and water as a solvent. It was measured using the Kuttle method. Species to be detected by this method is per full O Roo Kuta Noe Ichito (C 7 F 15 COO I).
  • the concentration of APF ⁇ in the waste water after coagulation after emulsion polymerization of PTFE was 148 ppm when measured.
  • the pH was adjusted to 10.0 by adding a 0.2 N aqueous solution of sodium hydroxide to this aqueous solution.
  • the liquid temperature was 26 ° C.
  • this solution 10 L (80 content 1. 48 g, 3. 43mmo 1) aluminum and mixed aqueous solution of chloride mug Neshiumu chloride [A 1 3+ ion concentration 0. 075mo 1 ZL, Mg 2+ ions 0. Approximately 229 mL [A 1 total ion amount 17.2 mmo 1, Mg 2+ total ion amount 34.3 mmo 1] was dropped over 2 hours.
  • the concentration of APFO was 2 ppm, and thus the fixation rate of PFOA contained in the layered double hydroxide was 98.6%.
  • a 10 mass% hydrochloric acid 10 0 g was added, After stirring at room temperature for 3 hours CF 2 C 1 CF 2 CHC 1 F / CF 3 CF 2 CHC 1 2 mixed medium (molar ratio 55/45, 30 g of Asahi Glass 225 (hereinafter, referred to as AK 225) was added and shaken vigorously for 10 minutes. After allowing this solution to stand and separate into two phases, the upper aqueous phase contained 0.14% by weight of PFOA and the lower AK225 phase contained 4.03% by weight of PFOA. The recovery rate from the original coagulated wastewater was 85.1%.
  • Aqueous mixed solution of aluminum chloride and zinc chloride [A13 + ion concentration 0.075mo1 / L, Zn2 + ion 0.15mo1ZL] Approx.45.8mL [Total amount of A13 + ion 3. 43 mmol, Zn 2+ ion total amount 6.86 mmol 1] was dropped over 2 hours. During the dropping, stirring was continued using an anchor blade so that the G value became 100 s _1 . During the addition of the metal ion aqueous solution, the coagulated waste water was bubbled with nitrogen gas at a constant flow rate of 1 Nm 3 Zm 3 ⁇ h to remove dissolved carbonate ions and carbon dioxide in the aqueous solution. During the dropping, add 0.2 N sodium hydroxide aqueous solution appropriately to adjust the pH to 6.5 or more.
  • Example 2 The same operation as in Example 1 was performed on the waste water after coagulation after the emulsion polymerization of PTFE as in Example 1 except that the pH was adjusted to 10.0 using potassium hydroxide instead of sodium hydroxide. .
  • the fixed rate of PFOA contained in the layered double hydroxide was 97.5%, and when AK 225 was extracted in the same manner as in Example 1, the recovery from the original wastewater was 84.1%. .
  • Example 2 The same operation as in Example 2 was performed on the waste water after coagulation after the emulsion polymerization of PTFE as in Example 2, except that the pH was adjusted to 7.0 using potassium hydroxide instead of sodium hydroxide. .
  • the fixed rate of PFO A contained in the layered double hydroxide was 98.6%, and when AK 225 was extracted in the same manner as in Example 1, the recovery from the original wastewater was 84.9%. there were.
  • Example 2 The same operation as in Example 1 was performed on the waste water after coagulation after the emulsion polymerization of PTFE as in Example 1 except that 30 g of trichloromethane was used as an extraction medium.Layered PFOA contained in double hydroxide The fixed rate was 98.1%, and the recovery rate from the original wastewater was 76.7% after trichloromethane extraction.
  • Example 5 The same operation as in Example 1 was performed on the waste water after coagulation after the emulsion polymerization of PTFE, except that 30 g of dichloromethane was used as the extraction medium. Fixation of PF OA contained in the layered double hydroxide The recovery was 97.8%, and the recovery from the original wastewater was 70.2% after dichloromethane extraction. [Example 5]
  • Example 2 The same fixing operation as in Example 1 was performed on the waste water after coagulation after the emulsion polymerization of PTFE as in Example 1.
  • the fixing rate of PFO A contained in the layered double hydroxide was 97.8%.
  • AK 225 extraction was performed in the same manner as in Example 1 except that 100 g of 3% by mass sulfuric acid was used instead of 100% of 10% by mass hydrochloric acid as a mineral acid used for dissolving the layered double hydroxide.
  • the recovery rate from the original wastewater was 83.7%
  • Example 2 The same fixing operation as in Example 1 was performed on the waste water after coagulation after the emulsion polymerization of PTF E as in Example 1.
  • the fixed rate of PFOA contained in the layered double hydroxide was 98.1%.
  • Extraction of AK225 was performed in the same manner as in Example 1 except that 100 g of 10% by mass of nitric acid was used instead of 100% of 10% by mass of hydrochloric acid as the mineral acid used for dissolving the layered double hydroxide.
  • the recovery rate from wastewater was 84.5%.
  • the pH was adjusted to 10.0 by adding a 0.2 N aqueous sodium hydroxide solution to distilled water.
  • the liquid temperature was 26 ° C.
  • a 1 3+ ions total 1 I .2 mmo1, Mg 2 + ion total amount of 34.3 mmo 13 was added dropwise over 2 hours.
  • the G value using an anchor blade was continued stirring such that the 100 s 1.
  • the coagulated wastewater was bubbled with nitrogen gas at a constant flow rate of 1 Nm 3 / m 3 ⁇ h to remove dissolved carbonate ions and carbon dioxide gas in the aqueous solution.
  • a 0.2 N aqueous sodium hydroxide solution was appropriately added dropwise to adjust the pH to 9.8 or more and 10.2 or less.
  • the extremely pale milky liquid began to aggregate and began to form a white precipitate.
  • the formation of the precipitate was completed. When the stirring was stopped, the precipitate formed slowly settled. The precipitate was collected by filtration through a membrane filter having an average diameter of 3 m.
  • PTFE water obtained by polymerizing TFE using APFO as an emulsifier PTFE is flocculated from the aqueous dispersion.
  • Coagulated wastewater after separation (SS component: 400 ppm, APF ⁇ concentration: 148 ppm, pH 4.5).
  • the precipitate was added and stirred at room temperature for 1 hour. When the stirring was stopped, the precipitate settled out slowly.
  • the precipitate was collected by filtration through a membrane filter having an average diameter of 3 m.
  • the concentration of APFO was 63 ppm, and therefore, the fixing ratio of PFOA contained in the layered double hydroxide was 57.4%.
  • the pH was adjusted to 10.0 by adding a 0.2 N aqueous sodium hydroxide solution to distilled water.
  • the liquid temperature was 26 ° C.
  • 1.82 g (17.2 mmo 1) of sodium carbonate was dissolved.
  • the total amount was 17.2 mmo, and Mg 2+ ion total amount 34.3 mmo 1] was added dropwise over 2 hours.
  • the coagulated wastewater was bubbled with nitrogen gas at a constant flow rate of 1 Nm 3 Zm 3 ⁇ h to remove dissolved carbonate ions and carbon dioxide gas in the aqueous solution.
  • the G value by using the anchor part is stirring was continued so that the 100 s 1.
  • a 0.2 N aqueous sodium hydroxide solution was appropriately added dropwise to adjust the pH to 9.8 or more and 10.2 or less.
  • the extremely pale milky liquid began to aggregate and began to form a white precipitate.
  • PTFE is coagulated from an aqueous dispersion of PTFE obtained by polymerizing TFE using APFO as an emulsifier.
  • Coagulated wastewater after separation (SS component is 400 ppm
  • the precipitate was collected by filtration through a membrane filter having an average diameter of 3 / im.
  • the concentration of APFO was 121 ppm, and therefore, the fixing rate of PFOA contained in the layered double hydroxide was 18.2%.
  • APFO was fixed to the layered double hydroxide in the same manner as in Example 1 with respect to the coagulated waste water after emulsion polymerization of PTFE as in Example 1.
  • Fixed rate of P FO A contained in the layered double hydroxide is 8% 97., followed by the same method as in Example 1 except for using 30 g of C HF 2 CH 2 CF 3 in place of AK 225 When the extraction operation was performed, the recovery rate from the original wastewater was 79.4%.
  • a fluorine-containing emulsifier can be economically recovered by a simple operation.

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  • Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

L'invention concerne un procédé de récupération d'un agent émulsifiant fluorochimique à partir d'un hydroxyde composite lamellaire provenant d'eaux usées, résultant d'une polymérisation pour une production de fluoropolymère, et contenant l'agent émulsifiant fluorochimique. Ce procédé consiste à produire un hydroxyde composite lamellaire contenant l'agent émulsifiant fluorochimique piégé entre des feuilles de celui-ci, à séparer l'hydroxyde composite lamellaire des eaux usées de coagulation, à dissoudre l'hydroxyde dans un acide minéral, et à extraire l'agent émulsifiant fluorochimique de la solution au moyen d'un hydrocarbure fluoré. Cet agent émulsifiant fluorochimique peut ainsi être récupéré de manière économique par le biais d'une procédure simple.
PCT/JP2003/000659 2002-01-25 2003-01-24 Procede de recuperation d'un agent emulsifiant fluorochimique WO2003066533A1 (fr)

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JP2002-16619 2002-01-25
JP2002368453A JP2003285076A (ja) 2002-01-25 2002-12-19 含フッ素乳化剤の回収法
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Cited By (2)

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CN105400956A (zh) * 2015-10-29 2016-03-16 赣州腾远钴业有限公司 一种锂离子电池回收产生的含氟含磷废水的处理方法
CN113710620A (zh) * 2019-04-26 2021-11-26 大金工业株式会社 水的处理方法和组合物

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JP4492612B2 (ja) * 2004-05-10 2010-06-30 ダイキン工業株式会社 処理対象物精製方法
JP4806978B2 (ja) * 2004-12-28 2011-11-02 ダイキン工業株式会社 水性液体精製方法及び含フッ素ポリマー水性分散液製造方法
JP2007002072A (ja) * 2005-06-22 2007-01-11 Daikin Ind Ltd ノニオン性界面活性剤水性組成物製造方法
EP2532423B1 (fr) * 2010-02-03 2015-04-22 Asahi Glass Company, Limited Procédé de récupération d'émulsifiants fluorés anioniques
EP2756884B1 (fr) * 2011-09-13 2018-04-25 Asahi Glass Company, Limited Procédé de récupération d'un émulsifiant fluoré anionique
CN114669083B (zh) * 2022-03-12 2024-01-02 信丰华锐钨钼新材料有限公司 一种n1923弱碱性萃取分离钨和钼有机相的方法

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WO1999062830A1 (fr) * 1998-06-02 1999-12-09 Dyneon Gmbh & Co. Kg Procede pour la recuperation d'acides alcanoiques fluores dans des eaux residuaires
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CN113710620A (zh) * 2019-04-26 2021-11-26 大金工业株式会社 水的处理方法和组合物

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