[go: up one dir, main page]

WO2013031848A1 - Procédé de décomposition d'un composé organique fluoré - Google Patents

Procédé de décomposition d'un composé organique fluoré Download PDF

Info

Publication number
WO2013031848A1
WO2013031848A1 PCT/JP2012/071871 JP2012071871W WO2013031848A1 WO 2013031848 A1 WO2013031848 A1 WO 2013031848A1 JP 2012071871 W JP2012071871 W JP 2012071871W WO 2013031848 A1 WO2013031848 A1 WO 2013031848A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
organic compound
containing organic
decomposing
compound
Prior art date
Application number
PCT/JP2012/071871
Other languages
English (en)
Japanese (ja)
Inventor
智行 藤田
佳奈 石川
森澤　義富
堀　久男
峻彦 坂本
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Publication of WO2013031848A1 publication Critical patent/WO2013031848A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method for decomposing a fluorine-containing organic compound with subcritical water.
  • the fluorine-containing organic compound is decomposed to recover a low-molecular-weight fluorine-containing compound (hydrogen fluoride, alkali metal fluoride, alkaline earth metal fluoride, etc.) having a molecular weight lower than that of the fluorine-containing organic compound. It has been proposed to reuse these as raw materials for fluorine-containing organic compounds. For example, the following method is disclosed. (1) A method of decomposing a fluorine-containing polymer having a sulfonic acid type functional group with subcritical water in the presence of iron powder (Patent Document 1).
  • Patent Document 2 A method in which a halogen-containing polymer is decomposed by mixing with supercritical water in the presence of a basic compound to obtain a low molecular weight hydrocarbon (Patent Document 2).
  • Patent Document 3 A method of decomposing organic fluorosulfonic acids or organic fluorocarboxylic acids with subcritical water in the presence of metal powder (Patent Document 3).
  • a fuel cell electrode containing a fluorinated polymer having a sulfonic acid type functional group and a catalyst metal is treated with supercritical water, and the fluorinated polymer having a sulfonic acid type functional group is decomposed to recover the catalyst metal.
  • JP 2010-059301 A Japanese Patent Laid-Open No. 10-088146 JP 2006-306736 A JP 2010-240542 A
  • iron powder having a mole number of moles or more of fluorine atoms contained in the fluorine-containing polymer having a sulfonic acid type functional group is required.
  • a large amount of iron is mixed. It takes time to purify the low molecular weight fluorine-containing compound, and it is difficult to implement industrially.
  • the reaction vessel since the supercritical water is used, the reaction vessel is easily corroded. Further, since a large amount of metal eluted from the corroded reaction vessel is mixed into the low molecular weight fluorine-containing compound, it takes time to purify the low molecular weight fluorine-containing compound, and it is difficult to implement industrially.
  • a metal powder having a mole number of 1 times or more of the number of moles such as organic fluorosulfonic acids is required, and the metal is mixed into the obtained low molecular weight fluorine-containing compound. It takes time to purify the low molecular weight fluorine-containing compound, and it is difficult to implement industrially.
  • the reaction vessel since supercritical water is used, the reaction vessel is easily corroded. In addition, a large amount of metal eluted from the corroded reaction vessel or electrode catalyst metal is mixed into the low molecular weight fluorine-containing compound. It takes time to purify the low molecular weight fluorine-containing compound, and it is difficult to implement industrially.
  • the present invention can efficiently decompose the fluorine-containing organic compound, suppress the corrosion of the reaction vessel, and contain less metal (excluding alkali metals and alkaline earth metals) in the obtained low molecular weight fluorine-containing compound. It aims at providing the decomposition
  • the present invention is a method for decomposing a fluorine-containing organic compound having the following configurations [1] to [9].
  • [1] A method for decomposing a fluorine-containing organic compound by bringing it into contact with subcritical water and molecular oxygen, wherein the amount of molecular oxygen present in the reaction system is the number of moles of carbon atoms contained in the fluorine-containing organic compound.
  • the subcritical water is substantially free of metal elements (excluding alkali metal elements and alkaline earth metal elements), and the temperature of the reaction system is 250 ° C.
  • the method for decomposing a fluorine-containing organic compound wherein the temperature is lower than 374.15 ° C.
  • the fluorine-containing polymer having a repeating unit derived from a hydrocarbon monomer is a fluorine-containing polymer having a repeating unit derived from ethylene or propylene and a repeating unit derived from fluoroethylenes, and has a sulfonic acid type functional group
  • [5] The method for decomposing a fluorine-containing organic compound according to any one of [1] to [4], wherein a compound capable of reacting with hydrogen fluoride is present.
  • [6] The method for decomposing a fluorine-containing organic compound according to [5], wherein the compound capable of reacting with hydrogen fluoride is at least one selected from the group consisting of a basic compound, sodium fluoride, and potassium fluoride.
  • the basic compound is an alkali metal oxide, an alkaline earth metal oxide, an alkali metal hydroxide, an alkaline earth metal hydroxide, or ammonia. .
  • [8] The method for decomposing a fluorine-containing organic compound according to any one of [1] to [7], comprising the following steps (i) to (iii): (I) The process of putting water and a fluorine-containing organic compound in reaction container. (Ii) A step of introducing a gas containing molecular oxygen into the reaction vessel. (Iii) A step of bringing the fluorine-containing organic compound into contact with subcritical water and molecular oxygen and decomposing it under pressure and temperature conditions in which water in the reaction vessel becomes subcritical water. [9] The method for decomposing a fluorine-containing organic compound according to [8], further comprising the following step (iv) after the step (iii). (Iv) A step of recovering decomposition products from the reaction vessel.
  • the fluorine-containing organic compound can be efficiently decomposed, corrosion of the reaction vessel can be suppressed, and the metal (however, alkali metal and alkaline earth) to the low molecular weight fluorine-containing compound obtained can be obtained.
  • the metal (however, alkali metal and alkaline earth) to the low molecular weight fluorine-containing compound obtained can be obtained.
  • the fluorine-containing organic compound can be efficiently decomposed in subcritical water.
  • the “supercritical water” in the present specification means water under pressure and temperature conditions at or above the critical point (pressure 22.12 MPa, temperature 374.15 ° C.).
  • the “subcritical water” in the present specification means water that is in a liquid state at a temperature of 100 ° C. or higher and lower than the critical temperature.
  • fluorinated organic compound in the present specification means an organic compound having one or more fluorine atoms in the molecule.
  • low molecular weight fluorine-containing compound in the present specification means an organic compound or inorganic compound obtained by decomposing a fluorine-containing organic compound, having a molecular weight lower than that of the fluorine-containing organic compound and having one or more fluorine atoms in the molecule. Means.
  • substantially no metal element is present in subcritical water means that metal ions (excluding alkali metal ions and alkaline earth metal ions) in subcritical water are 10,000 ppm or less, metal powder (Excluding alkali metal powders and alkaline earth metal powders) is 10,000 ppm or less, and metal oxides (however, excluding alkali metal oxides and alkaline earth metal oxides) are contained in 10,000 ppm or less. Means state.
  • repeating unit means a unit derived from a monomer formed by polymerization of the monomer.
  • the repeating unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
  • the “monomer” in the present specification means a compound having a polymerization-reactive carbon-carbon double bond.
  • the “sulfonic acid type functional group” means a sulfo group (—SO 3 H) or a functional group that can be converted into a sulfo group by hydrolysis or neutralization.
  • the functional group can be converted into a sulfo group, -SO 3 M (however, M is an alkali metal or a quaternary ammonium salt.), - SO 2 F, -SO 2 Cl, -SO 2 Br or the like can be mentioned It is done.
  • the “carboxylic acid type functional group” in the present specification means a carboxy group (—COOH) or a functional group that can be converted into a carboxy group by hydrolysis or neutralization.
  • Examples of the functional group that can be converted to a carboxy group include —CN, —COF, —COOR 1 (where R 1 is an alkyl group having 1 to 10 carbon atoms), —COOM (where M is an alkali metal or A quaternary ammonium base), —COONR 2 R 3 (wherein R 2 and R 3 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 and R 3 may be the same) And may be different).
  • the method for decomposing a fluorine-containing organic compound of the present invention is a reaction system in which molecular oxygen is present and a metal element is not substantially present in subcritical water, and the fluorine-containing organic compound is contacted with subcritical water and molecular oxygen. This is a method of disassembling.
  • fluorine-containing organic compounds examples include fluorine-containing polymers, organic fluorosulfonic acids, and organic fluorocarboxylic acids.
  • the organic fluorosulfonic acids are preferably fluorine-containing polymers having a sulfonic acid type functional group, and the organic fluorocarboxylic acids are also preferably fluorine-containing polymers having a carboxylic acid type functional group.
  • the method for decomposing a fluorine-containing organic compound of the present invention is a method for decomposing a fluorine-containing polymer having a number average molecular weight (Mn) of 1,000 or more, which has been difficult to dispose of by conventional disposal methods such as incineration. It is particularly useful.
  • the number average molecular weight (Mn) can be measured by size exclusion chromatography or melt dynamic shear rate measurement.
  • the organic fluorosulfonic acids are preferably fluorine-containing polymers having a sulfonic acid type functional group having a number average molecular weight of 1,000 or more.
  • the organic fluorocarboxylic acids are preferably fluorine-containing polymers having a carboxylic acid type functional group having a number average molecular weight of 1,000 or more.
  • the fluorine-containing polymer may have any repeating unit derived from a monomer having one or more fluorine atoms.
  • Polyfluoroalkylethylenes having a fluoroalkyl group having 2 to 12 carbon atoms: CF 3 CF 2 CH ⁇ CH 2 , CF 3 CF 2 CF 2 CF 2 CH ⁇ CH 2 , CF 3 CF 2 CF 2 CF 2 CF ⁇ CH 2, CF 2 HCF 2 CF 2 CF CH 2 and the like.
  • Perfluorovinyl ethers having a carboxylic acid type functional group YCF 2 CF 2 CF 2 OCF ⁇ CF 2 (where Y is a carboxylic acid type functional group) and the like.
  • Perfluorovinyl ethers having a sulfonic acid type functional group ZCF 2 CF 2 OCF (CF 3 ) CF 2 OCF ⁇ CF 2 (where Z is a sulfonic acid type functional group) and the like.
  • the fluorine-containing polymer preferably has a repeating unit derived from a monomer having no fluorine atom in that it can be efficiently decomposed.
  • a fluorine-containing polymer having a sulfonic acid type functional group is preferable.
  • a hydrocarbon-type monomer is preferable and the following monomer is mentioned. Hydrocarbon monomers: ethylene, propylene, isobutene, 1-butene and the like.
  • fluorine-containing polymer having a repeating unit derived from a hydrocarbon-based monomer a fluorine-containing polymer having a repeating unit derived from ethylene or propylene is preferable, and a repeating unit derived from ethylene or propylene and fluoroethylenes (tetrafluoroethylene is preferred).
  • a fluorine-containing polymer having a repeating unit derived from (preferably) is more preferable.
  • an ethylene / tetrafluoroethylene copolymer hereinafter referred to as ETFE
  • ETFE may have a repeating unit derived from a hydrocarbon monomer other than ethylene and a repeating unit derived from a monomer having one or more fluorine atoms other than CF 2 ⁇ CF 2 .
  • a tetrafluoroethylene / sulfonic acid functional group-containing perfluorovinyl ether copolymer having a repeating unit derived from a perfluorovinyl ether having a functional group is particularly preferred.
  • the number average molecular weight of the fluorine-containing polymer is preferably 1,000 to 1,000,000,000 from the viewpoint of the usefulness of the method for decomposing the fluorine-containing organic compound of the present invention.
  • the number average molecular weight of the more preferable fluorine-containing polymer is 2,000 or more.
  • T Q serving as an index of molecular weight is preferably 100 ° C. or higher from the viewpoint of the usefulness of the method for decomposing a fluorine-containing organic compound of the present invention.
  • a temperature of ⁇ 300 ° C. is particularly preferred.
  • T Q is a temperature (° C.) indicating a capacity flow rate of 100 mm 3 / sec.
  • the capacity flow rate is obtained by causing the fluorine-containing polymer to melt and flow out from a nozzle having a length of 1 mm and an inner diameter of 1 mm under a pressure of 2.94 MPa, and the outflowing fluorine-containing polymer is expressed in units of mm 3 / sec.
  • the higher the TQ the higher the molecular weight.
  • the form of the fluoropolymer is not particularly limited. Specifically, a powder, a pellet, a molded object (a film, an O-ring, packing, etc.) etc. are mentioned. In order for the decomposition reaction to proceed rapidly, the form of the fluoropolymer is preferably a powder.
  • the fluorine-containing polymer in the form of a molded body or the like is preferably pulverized into a powder and used for the decomposition method of the present invention.
  • the fluorine-containing organic compound may be composed of only one kind or a mixture of two or more kinds.
  • the fluorine-containing organic compound may be a composition with other materials. It may be coated. Specifically, it is coated with a composition with an inorganic material (carbon, silica, etc.), a composition with a low molecular weight and / or high molecular weight organic compound not containing a fluorine atom, and other materials (paper, fiber, plastic, etc.). And a dispersion in water and / or an organic solvent.
  • the content of the fluorine-containing organic compound is preferably 0.01 to 50 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of water from the viewpoint of economy. If the amount of the fluorine-containing organic compound is not less than the lower limit of the above range, the low molecular weight fluorine-containing compound can be sufficiently recovered. If the amount of the fluorinated organic compound is not more than the upper limit of the above range, the fluorinated organic compound can be decomposed more efficiently.
  • the water that becomes subcritical water excludes impurities eluted from the reaction vessel and the object to be treated, and excludes metal elements derived from catalytic metals (iron powder, etc.) (however, alkali metal elements and alkaline earth metal elements). ) Is not substantially present. If the metal element is not substantially present in the water, the metal (however, excluding alkali metals and alkaline earth metals) is mixed into the low molecular weight fluorine-containing compound obtained by the decomposition reaction.
  • the amount of molecular oxygen present in the reaction system before the decomposition reaction is at least 1 mol of the number of moles of carbon atoms contained in the fluorine-containing organic compound, preferably at least 1.5 times mol, preferably at least 2 times mol. Particularly preferred.
  • the upper limit of the amount of molecular oxygen is not particularly limited, but is preferably about 10 moles in view of economy and the like. If the amount of molecular oxygen is 1 mol or more of the number of moles of carbon atoms contained in the fluorine-containing organic compound, the fluorine-containing organic compound can be decomposed to carbon dioxide, and hydrocarbons contained in the decomposition products are reduced. It can be reduced sufficiently.
  • An inert gas such as nitrogen gas or inert gas other than molecular oxygen may be present in the reaction system.
  • the gas introduced into the reaction vessel may be pure oxygen gas, air, or a mixed gas of oxygen gas and inert gas.
  • the number of moles of carbon atoms contained in the fluorinated organic compound is determined by a known method to determine the proportion of the fluorinated organic compound contained in the decomposition target, and the number of moles of carbon atoms contained in the fluorinated organic compound is determined by a known analysis method. It can be determined by quantifying by (elemental analysis etc.).
  • a compound capable of reacting with hydrogen fluoride in the reaction system, a compound capable of reacting with hydrogen fluoride can be present if necessary.
  • the compound capable of reacting with hydrogen fluoride is used for efficiently recovering hydrogen fluoride as a fluoride salt from the decomposition product obtained by decomposition of the fluorine-containing organic compound.
  • Compounds that can react with hydrogen fluoride include basic compounds (alkali metal oxides, alkaline earth metal oxides, alkali metal hydroxides, alkaline earth metal hydroxides, ammonia, etc.), fluorine Examples thereof include compounds that form a hydride adduct (sodium fluoride, potassium fluoride, etc.).
  • the amount of the compound capable of reacting with hydrogen fluoride is preferably from 0 to 1,200 parts by weight, particularly preferably from 0 to 600 parts by weight, based on 100 parts by weight of the fluorine-containing organic compound, from the viewpoint of economy.
  • the temperature of the reaction system is 250 ° C. or higher and lower than 374.15 ° C., preferably 300 ° C. or higher and lower than 374.15 ° C., particularly preferably 320 ° C. or higher and lower than 374.15 ° C.
  • the temperature of the reaction system is 250 ° C. or higher, the fluorine-containing organic compound can be efficiently decomposed in subcritical water. If the temperature of the reaction system is less than 374.15 ° C., water does not become supercritical water, and therefore corrosion of the reaction vessel can be suppressed.
  • the pressure in the reaction system may be a pressure at which the water in the reaction system becomes subcritical water at the above temperature.
  • the contact time between the fluorinated organic compound and the subcritical water may be appropriately determined according to the amount, temperature, pressure, etc. of the fluorinated organic compound.
  • the contact time is preferably 1 to 24 hours, particularly preferably 1 to 10 hours. In the case of a fluorine-containing organic compound other than the fluorine-containing polymer, it may be decomposed in a shorter time.
  • decomposition product examples of the decomposition products generated by the decomposition reaction include water, carbon dioxide, and low molecular weight fluorine-containing compounds. Depending on the reaction conditions of the decomposition reaction and the fluorine-containing organic compound, in addition to the low molecular weight fluorine-containing compound, hydrocarbons, materials that cannot be decomposed by subcritical water, and the like may be included.
  • hydrogen fluoride is generated by the decomposition of the fluorine-containing organic compound, if a compound that can react with the hydrogen fluoride is present in the reaction system, a reaction product of the compound and hydrogen fluoride (basic compound) Fluoride and hydrogen fluoride adduct of sodium fluoride are produced. In the present invention, this reaction product is also regarded as a decomposition product.
  • Low molecular weight fluorine-containing compounds examples include a low molecular weight fluorine-containing organic compound and a low molecular weight fluorine-containing inorganic compound.
  • a low molecular weight fluorine-containing inorganic compound is particularly preferable because it can be easily reused as a raw material for hydrogen fluoride, a fluorine-containing organic compound, or the like.
  • the molecular weight of the low molecular weight fluorine-containing organic compound, which is a decomposition product thereof is 20 to 900 because it can be easily reused as a raw material for hydrogen fluoride, a fluorine-containing organic compound, etc.
  • 20 to 100 is more preferable, and 20 to 80 is particularly preferable.
  • the molecular weight of the low molecular weight fluorine-containing organic compound, which is a decomposition product thereof is not particularly limited as long as it is lower than the molecular weight of the fluorine-containing organic compound before decomposition.
  • low molecular weight fluorine-containing organic compound examples include fluoroethylenes, fluoropropylenes, polyfluoroalkylethylenes, perfluorovinyl ethers, carboxylic acid type functional groups or sulfonic acid type functional groups described as monomers having one or more fluorine atoms.
  • Organic fluorocarboxylic acids having a molecular weight of less than 1,000 (CF 3 COOH, CF 2 HCOOH, CFH 2 COOH, HOCOCF 2 COOH, etc.), organic fluorosulfonic acids having a molecular weight of less than 1,000 (CF 3 SO 3 H, CF 2 HSO 3 H, CFH 2 SO 3 H, HO (C ⁇ O) CF 2 SO 3 H, etc.), fluorinated aliphatic hydrocarbons (perfluorocarbons having 1 to 10 carbon atoms, carbon number) 1-10 hydrofluorocarbons, carbon Chlorofluorocarbons 1-10 include hydrochlorofluorocarbons, etc.) and the like having 1 to 10 carbon atoms.
  • Examples of the low molecular weight fluorine-containing inorganic compound include hydrogen fluoride, elemental fluorine, alkali metal fluoride, alkaline earth metal fluoride, ammonium fluoride, and the like.
  • alkali metal fluoride, alkaline earth metal fluoride, ammonium fluoride, etc. when a compound capable of reacting with hydrogen fluoride is present in the decomposition reaction system, hydrogen fluoride produced by the decomposition reaction is the reaction system.
  • the decomposition product produced by reacting with the compound The recovered alkali metal fluoride, alkaline earth metal fluoride, ammonium fluoride and the like can be reused as a source of hydrogen fluoride.
  • the obtained low-molecular-weight fluorine-containing compound is calcium fluoride
  • it is regenerated as a hydrogen fluoride source by a known method (JP 2010-194468 and the method described in the prior art document described therein). Available.
  • the reaction vessel for performing the decomposition reaction may be any one that can withstand the pressure and temperature conditions in the reaction system and subcritical water.
  • hydrogen fluoride generated by the decomposition of the fluorine-containing organic compound
  • those that can withstand hydrofluoric acid are preferred.
  • the material for the reaction vessel include stainless steel, hastelloy, and Inconel.
  • stirring means in the reaction vessel examples include known stirring means such as a magnetic stirrer and a stirrer with stirring blades.
  • the material in contact with hydrofluoric acid is a material that can withstand hydrofluoric acid.
  • the following pre-process and post-process are preferably performed. Specifically, there is a method in which the following steps (i) to (iii) are sequentially performed. Furthermore, it is preferable to perform the following step (iv) after step (iii).
  • the following step (iii) is a step for carrying out the decomposition method of the present invention.
  • (I) The process of putting water and a fluorine-containing organic compound in reaction container.
  • a step of recovering decomposition products from the reaction vessel is preferably performed. Specifically, there is a method in which the following steps (i) to (iii) are sequentially performed. Furthermore, it is preferable to perform the following step (iv) after step (iii).
  • the following step (iii) is
  • Step (i) is a step of putting water and a fluorine-containing organic compound in the reaction vessel. It is also preferable to put a compound capable of reacting with hydrogen fluoride as needed in the reaction vessel. It is preferable to bring the contents into contact with the stirring means.
  • Step (ii) is a step of introducing a gas containing molecular oxygen into the reaction vessel.
  • the pressure in the reaction vessel may be set to a pressure at which the water becomes subcritical water at the temperature in step (iii) as necessary.
  • Step (iii) is a step for carrying out the decomposition method of the present invention.
  • a gas containing molecular oxygen in the reaction vessel or a gas for maintaining the pressure in the reaction vessel at a predetermined pressure may be introduced continuously or intermittently as necessary.
  • the amount of molecular oxygen present in the reaction vessel including that consumed by the decomposition of the fluorine-containing organic compound is introduced by introducing a gas containing molecular oxygen.
  • the amount of molecular oxygen in the gas (air) that was present in the reaction vessel before the reaction, and the amount of molecular oxygen in the gas introduced into the reaction vessel from step (ii) to step (iii) Can be obtained from
  • Step (iv) is a step of recovering the decomposition product from the reaction vessel.
  • the decomposition product contains a low molecular weight fluorine-containing compound.
  • a low molecular weight fluorine-containing compound is further recovered from the decomposition product as necessary.
  • the pre-process and post-process for carrying out the decomposition method of the present invention are not limited to the above-mentioned process (i), process (ii), and process (iv).
  • water may be introduced simultaneously with or after the introduction of the gas containing molecular oxygen in the step (ii) without introducing water into the reaction vessel in the step (i).
  • the fluorine-containing organic compound can be put into the reaction vessel.
  • Example 1 to 4 and 8 are examples
  • Example 5 is a reference example
  • Examples 6 and 7 are comparative examples.
  • Compound 5 (1,3-dichloro-1,1,2,2,3-pentafluoropropane): CClF 2 CF 2 CHClF
  • Compound 6 (1,1-dichloro-1-fluoroethane): CH 3 CCl 2 F
  • Compound 7 (1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane): C 6 F 13 H
  • Compound 8 (t-butyl peroxypivalate. Perbutyl PV manufactured by NOF Corporation): (CH 3 ) 3 COO—OC (CH 3 ) 3
  • T Q Flow Tester CFT-500D manufactured by Shimadzu Corporation fluoropolymer was measured using (1) was 225 ° C..
  • the ion exchange capacity of the fluoropolymer (1) determined by titration was 1.10 meq / g.
  • the internal temperature was cooled to room temperature, the remaining compounds 2 and 3 were purged, and the autoclave was opened.
  • the obtained slurry of the fluoropolymer (2) in the autoclave was washed with the compound 5, filtered through a glass filter and dried to obtain 64.8 g of a powder of the fluoropolymer (2).
  • the fluoropolymer (2) was ETFE.
  • the number average molecular weight (Mn) of the fluoropolymer (2) determined by melt dynamic shear rate measurement was 320,000. Melt dynamic shear rate measurements are described in Tuminello, W. et al. H. , Polym. Eng. Sci. , 26, 1339-1347 (1986) or Tuminello, W. et al. H.
  • the volume flow rate (Q value) of the fluoropolymer (2) was 7.3 mm 3 / sec, and the melting point was 281 ° C.
  • the capacity flow rate (Q value) is a capacity of the fluorine-containing polymer (2) flowing out from a nozzle having a diameter of 2.095 mm and a length of 8 mm under a load of 297 ° C. and 0.7 MPa using a high / low flow tester. (Mm 3 / sec).
  • the melting point is a melting peak when the temperature is raised at a rate of 10 ° C./min using a SII DSC 6220 type differential scanning calorimeter (Seiko Electronics Co., Ltd.).
  • a propylene-tetrafluoroethylene copolymer (hereinafter referred to as fluoropolymer (3)) was obtained according to the production method described in JP-A-55-127212.
  • the number average molecular weight (Mn) of the fluorine-containing polymer (3) determined by size exclusion chromatography was 160,000.
  • the method described in the international publication 2011/055760 was used for the measuring method by size exclusion chromatography.
  • Step (iii) It heated over 1 hour until the temperature in an autoclave became 350 degreeC with the oil bath, the water in an autoclave was made into subcritical water, and it stirred with the stirring blade at this temperature for 6 hours. Next, the autoclave was cooled to room temperature and then opened.
  • Example 2 The decomposition reaction was performed in the same manner as in Example 1 except that the powder of the fluoropolymer (2) was used instead of the fluoropolymer (1). As a result, 70.5% of the fluorine atoms contained in the used fluoropolymer (2) were recovered as fluoride ions (hydrogen fluoride). No corrosion was observed on the inner surface of the autoclave.
  • Example 3 The decomposition reaction was performed in the same manner as in Example 1 except that the powder of the fluoropolymer (3) was used instead of the fluoropolymer (1). As a result, 85.2% of the fluorine atoms contained in the used fluoropolymer (3) were recovered as fluoride ions (hydrogen fluoride). No corrosion was observed on the inner surface of the autoclave.
  • Example 4 The decomposition reaction was performed in the same manner as in Example 1 except that 106 mg of calcium hydroxide was further added to the autoclave in step (i). As a result, 65.0 mg of calcium fluoride was obtained. This value corresponds to the recovery of 59.3% of the fluorine atoms contained in the fluoropolymer (1) used as calcium fluoride. In addition, corrosion was not confirmed on the inner surface of the autoclave.
  • Example 5 The decomposition reaction was performed in the same manner as in Example 1 except that the temperature in the autoclave in step (iii) was changed from 350 ° C to 380 ° C. As a result, 70.1% of fluorine atoms contained in the used fluoropolymer (1) were recovered as fluoride ions (hydrogen fluoride). In addition, corrosion was confirmed on the inner surface of the autoclave.
  • Example 6 A decomposition reaction was attempted in the same manner as in Example 1 except that argon gas was introduced instead of oxygen gas in step (ii). As a result, 15.1% of the fluorine atoms contained in the used fluoropolymer (1) was recovered as fluoride ions (hydrogen fluoride).
  • Example 7 A decomposition reaction was attempted in the same manner as in Example 1 except that ion-exchanged water was not added to the autoclave in step (i). As a result, 0.8% of fluorine atoms contained in the used fluoropolymer (1) were recovered as fluoride ions (hydrogen fluoride).
  • Example 8 A decomposition reaction was attempted in the same manner as in Example 1 except that polyvinylidene fluoride (manufactured by Synquest) was used in place of the fluoropolymer (1) in step (i). As a result, 98% of the fluorine atoms contained in the used polyvinylidene fluoride were recovered as fluoride ions (hydrogen fluoride).
  • Example 1 to 4 and 8 the fluorine-containing organic compound could be efficiently decomposed, and corrosion of the reaction vessel was suppressed.
  • Example 5 using supercritical water the fluorine-containing organic compound could be efficiently decomposed, but part of the reaction vessel was corroded.
  • Example 6 in which molecular oxygen was not used and Example 7 in which water was not used the fluorine-containing organic compound could not be efficiently decomposed.
  • fluorine can be efficiently recovered as a low molecular weight fluorine-containing compound from a fluorine-containing organic compound such as a used fluorine-containing polymer or a material containing the fluorine-containing organic compound.
  • a fluorine-containing organic compound such as a used fluorine-containing polymer or a material containing the fluorine-containing organic compound.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • General Chemical & Material Sciences (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Cette invention concerne un procédé de décomposition d'un composé organique fluoré qui permet de décomposer le composé organique fluoré à une efficacité élevée, pour empêcher la corrosion d'un réacteur, et pour réduire la contamination du composé fluoré de bas poids moléculaire obtenu par un métal (exclusions faites d'un métal alcalin et d'un métal alcalino-terreux). Le procédé de décomposition d'un composé organique fluoré selon l'invention comprend la mise en contact du composé organique fluoré avec de l'eau sous-critique et de l'oxygène moléculaire, la quantité d'oxygène moléculaire dans le système réactionnel étant d'une fois en mole ou plus le nombre molaire d'atomes de carbone contenus dans le composé organique fluoré, sensiblement en l'absence de tout élément métallique (exclusions faites d'un métal alcalin et d'un métal alcalino-terreux) dans l'eau sous-critique, et à une température de système réactionnel de 250°C ou plus et inférieure à 374,15°C.
PCT/JP2012/071871 2011-09-02 2012-08-29 Procédé de décomposition d'un composé organique fluoré WO2013031848A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-191547 2011-09-02
JP2011191547 2011-09-02
JP2012139965A JP2014210826A (ja) 2011-09-02 2012-06-21 含フッ素有機化合物の分解方法
JP2012-139965 2012-06-21

Publications (1)

Publication Number Publication Date
WO2013031848A1 true WO2013031848A1 (fr) 2013-03-07

Family

ID=47756328

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/071871 WO2013031848A1 (fr) 2011-09-02 2012-08-29 Procédé de décomposition d'un composé organique fluoré

Country Status (2)

Country Link
JP (1) JP2014210826A (fr)
WO (1) WO2013031848A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021155478A (ja) * 2020-03-25 2021-10-07 学校法人神奈川大学 フッ素原子含有ポリマーの分解方法、及びフッ素原子含有ポリマーの分解装置
EP4277723A4 (fr) * 2021-01-15 2024-07-10 University of Washington Système hydrothermique pour le traitement de sous-produits de régénération d'adsorbant
WO2025183031A1 (fr) * 2024-02-26 2025-09-04 ダイキン工業株式会社 Composition ainsi que procédé de fabrication de celle-ci, et procédé de fluoration

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7658557B2 (ja) * 2021-03-11 2025-04-08 学校法人帝京大学 ハロゲン化アルカリ金属の製造方法及びハロゲン化物の製造方法
JP7258319B1 (ja) * 2021-10-29 2023-04-17 学校法人神奈川大学 フッ素原子含有ポリマーの分解方法、及びフッ素原子含有ポリマーの分解装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09501458A (ja) * 1993-08-11 1997-02-10 ザ ユニバーシティ オブ アクロン 解重合法
JPH1088146A (ja) * 1996-09-20 1998-04-07 Kanegafuchi Chem Ind Co Ltd ハロゲン含有樹脂の油化処理方法
JP2002138057A (ja) * 2000-10-27 2002-05-14 Ishikawajima Harima Heavy Ind Co Ltd ハロゲン系有機廃棄物の処理方法および処理装置
JP2005343914A (ja) * 2004-05-31 2005-12-15 Ishikawajima Harima Heavy Ind Co Ltd プラスチック処理装置及びプラスチック処理方法
JP2010059301A (ja) * 2008-09-03 2010-03-18 National Institute Of Advanced Industrial Science & Technology フッ素系イオン交換樹脂膜の分解方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09501458A (ja) * 1993-08-11 1997-02-10 ザ ユニバーシティ オブ アクロン 解重合法
JPH1088146A (ja) * 1996-09-20 1998-04-07 Kanegafuchi Chem Ind Co Ltd ハロゲン含有樹脂の油化処理方法
JP2002138057A (ja) * 2000-10-27 2002-05-14 Ishikawajima Harima Heavy Ind Co Ltd ハロゲン系有機廃棄物の処理方法および処理装置
JP2005343914A (ja) * 2004-05-31 2005-12-15 Ishikawajima Harima Heavy Ind Co Ltd プラスチック処理装置及びプラスチック処理方法
JP2010059301A (ja) * 2008-09-03 2010-03-18 National Institute Of Advanced Industrial Science & Technology フッ素系イオン交換樹脂膜の分解方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021155478A (ja) * 2020-03-25 2021-10-07 学校法人神奈川大学 フッ素原子含有ポリマーの分解方法、及びフッ素原子含有ポリマーの分解装置
JP7501866B2 (ja) 2020-03-25 2024-06-18 学校法人神奈川大学 フッ素原子含有ポリマーの分解方法、及びフッ素原子含有ポリマーの分解装置
EP4277723A4 (fr) * 2021-01-15 2024-07-10 University of Washington Système hydrothermique pour le traitement de sous-produits de régénération d'adsorbant
WO2025183031A1 (fr) * 2024-02-26 2025-09-04 ダイキン工業株式会社 Composition ainsi que procédé de fabrication de celle-ci, et procédé de fluoration

Also Published As

Publication number Publication date
JP2014210826A (ja) 2014-11-13

Similar Documents

Publication Publication Date Title
JP7367817B2 (ja) フルオロスルホニル基含有化合物、フルオロスルホニル基含有モノマー及びそれらの製造方法
Puts et al. Polytetrafluoroethylene: synthesis and characterization of the original extreme polymer
JP5986102B2 (ja) マイクロエマルジョン及びマイクロエマルジョンを用いて作製されたフルオロポリマー
WO2013031848A1 (fr) Procédé de décomposition d'un composé organique fluoré
WO2014069165A1 (fr) Procédé de préparation d'un copolymère fluoré
KR101636350B1 (ko) 함불소 비닐에테르의 제조방법
JP7287404B2 (ja) フルオロスルホニル基含有含フッ素ポリマーの製造方法、塩型スルホン酸基含有含フッ素ポリマーの製造方法および酸型スルホン酸基含有含フッ素ポリマーの製造方法
JP7148787B2 (ja) 新規含フッ素化合物
JP2010523617A (ja) カルボニルパーフルオロポリエーテルを調製する方法
CN105358592B (zh) 含氟聚合物的制造方法
Thomas et al. Synthesis of 3, 6-dioxa-Δ7-4-trifluoromethyl perfluorooctyl trifluoromethyl sulfonimide: bis [(perfluoroalkyl) sulfonyl] superacid monomer and polymer
KR101751656B1 (ko) 불화메탄의 제조 방법
WO2012173153A1 (fr) Procédé de production d'un copolymère contenant du fluor
JP5851027B2 (ja) 新規なフッ化不飽和化合物及び該化合物から得られるポリマー
CN107001212A (zh) 制备含卤代氟化醚的化合物的方法
EP2238123A1 (fr) Réaction d'addition à du fluoroallylfluorosulfate
JP2013501022A (ja) ジフルオロ酢酸エステルの製造方法
CN111378064B (zh) 一种全氟磺酰氟树脂的制备方法
CN108884015A (zh) 用于制造氟化化合物的方法
JPWO2017086465A1 (ja) ヨウ素原子含有量の低減された含フッ素化合物を製造する方法
JP5842919B2 (ja) スルホ基を有する有機化合物の製造方法、液状組成物の製造方法およびフルオロスルホニル基を有する有機化合物の加水分解処理方法
JP4526826B2 (ja) フルオロハロゲンエーテルの製造方法
JP2013064105A (ja) スルホン酸型官能基を有する含フッ素ポリマーの分解方法
CN114096521A (zh) 全氟酰基过氧化物的制造方法及氟烷基碘的制造方法
JP4336141B2 (ja) −ｏｃｆ２ｈ、−ｏｃｆ２ｃｆ２ｈ、−ｏｃｆ（ｃｆ３）ｈの末端基を有するパーフルオロポリオキシアルキレンの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12827619

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12827619

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP