WO2005065800A1 - Procede de separation de tensioactif contenant du fluor - Google Patents

Procede de separation de tensioactif contenant du fluor Download PDF

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Publication number
WO2005065800A1
WO2005065800A1 PCT/US2004/043528 US2004043528W WO2005065800A1 WO 2005065800 A1 WO2005065800 A1 WO 2005065800A1 US 2004043528 W US2004043528 W US 2004043528W WO 2005065800 A1 WO2005065800 A1 WO 2005065800A1
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Prior art keywords
aqueous phase
fluorine
organic phase
containing surfactant
phase
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PCT/US2004/043528
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English (en)
Inventor
Tadahiro Yabu
Takuya Ichida
William G. O'brien
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Daikin Industries, Ltd.
E.I. Du Pont De Nemours And Company
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Application filed by Daikin Industries, Ltd., E.I. Du Pont De Nemours And Company filed Critical Daikin Industries, Ltd.
Publication of WO2005065800A1 publication Critical patent/WO2005065800A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used

Definitions

  • This invention relates to a process for separating a fluorine-containing surfactant from a processing object, and also relates to a process for recover the fluorine- containing surfactant from the processing object.
  • the processing object is a fluid as an aqueous or organic phase which includes the fluorine-containing surfactant.
  • Fluorine-containing surfactant is used as an emulsifier or a flocculation stabilizer in an emulsion polymerization process for producing polymer. It is necessary to separate and recover the fluorine-containing surfactant from process water (or waste water) as an aqueous phase in view of its cost and also in view of environmental considerations since the fluorine-containing surfactant is not biodegradable.
  • a method of membrane filtration by using a reverse osmotic membrane Japanese Patent Kokai Publication No. 2002-58966 and WO 2002/01 3953
  • a method of adsorption by using an ion exchange resin Japanese Patent Kokai
  • aqueous phase may contain the fluorine-containing surfactant and also polymer particles which do not flocculate in the aqueous phase, fouling of the membrane or the resin is likely to be caused by the polymer particles, and the membrane or the resin has to be replaced as the fouling occurs. Therefore, these methods have a disadvantage in cost. Otherwise, it will be necessary to remove the polymer particles from the aqueous phase before the filtration by the membrane or the adsorption by the ion exchange resin.
  • the inventors have studied a process of a liquid-liquid extraction by contacting an aqueous solution and an organic solvent, one of which is a processing object containing fluorine-containing surfactant, in order to separate and/or recover the fluorine-containing surfactant, and have completed the present invention.
  • the basic concept of the present invention is extraction of the fluorine- containing surfactant from the aqueous phase into the organic phase or from the organic phase into the aqueous phase by controlling the pH of the aqueous phase.
  • the extraction of the fluorine-containing surfactant from the aqueous phase into the organic phase does not occur significantly when the aqueous phase is about neutral or alkaline, but the extraction occurs significantly by making the aqueous solution acidic.
  • the organic phase after extraction i.e. the extract
  • the raffinate has a lowered concentration of the fluorine-containing surfactant by the extracted portion thereof
  • the extraction of the fluorine-containing surfactant from the organic phase into the aqueous phase does not occur significantly when the aqueous phase is strongly acidic, but the extraction occurs significantly when the aqueous solution is about neutral or alkaline.
  • the aqueous phase after extraction includes the extracted fluorine-containing surfactant, and the organic phase after extraction has a lowered concentration of the fluorine-containing surfactant by the extracted portion thereof.
  • the extraction of the surfactant from the aqueous phase into the organic phase and the extraction from the organic phase into the aqueous phase of the present invention can be conducted independently, these extractions can be combined by conducting first the former extraction and then the latter extraction.
  • the former extraction is understood to be a positive extraction
  • the latter extraction is understood to be a back extraction.
  • the organic phase which has been contacted with the first aqueous phase on the positive extraction is used as the organic phase to be contacted with the second aqueous phase on the back extraction.
  • the fluorine-containing surfactant can be recovered from the first aqueous phase to the second aqueous phase.
  • the polymer particles remain in the first aqueous phase in contrast to the surfactant, or move from the aqueous phase to the organic phase together with the surfactant during the positive extraction.
  • the polymer particles which have been included in the organic phase before the back extraction remain in the organic phase while the fluorine-containing surfactant is moved to the other aqueous phase. Therefore, the fluorine-containing surfactant and the polymer particles can be separated into different two phases by the positive extraction or by the back-extraction.
  • the one phase which contains the surfactant is subjected to an appropriate step (e.g. distillation or filtration by a membrane, or adsorption by an ion exchange resin), and thereby the surfactant is recovered as a surfactant concentrated phase which is substantially free of polymer particles.
  • an appropriate step e.g. distillation or filtration by a membrane, or adsorption by an ion exchange resin
  • the back extraction is not necessary when the surfactant is recovered by distillation from the organic phase that is obtained by the positive extraction.
  • These features of the extraction can be effected by using an organic compound which is immiscible in water.
  • immiscible in water is meant that that the organic compound does not mix with water to form a homogeneous mixture, i.e., two phases will be present.
  • the organic compound can range from being substantially insoluble to somewhat soluble in water under the conditions employed. As explained in more detail hereinaf er, when it is desired to limit the quantity of organic compound which will move into the aqueous phase during extraction, it is preferred to use organic compounds which are substantially insoluble in or slightly soluble in water.
  • the process of the present invention can be conducted continuously or in a batch-wise mode.
  • Fig. 1 shows a graph of an extraction ratio versus a pH value which was obtained from Example 6.
  • the process comprising: contacting the first aqueous phase with a first organic phase (i.e.
  • an extraction solvent including an organic compound which is immiscible in water so as to move the fluorine-containing surfactant from the first aqueous phase to the first organic phase, and thereby obtaining an aqueous phase having a lowered concentration of the fluorine-containing surfactant as a second aqueous phase (i.e. a raffinate) and an organic phase including the moved fluorine-containing surfactant as a second organic phase (i.e. an extract), and the first aqueous phase having a first pH value when it is contacted with the first organic phase.
  • an extraction solvent including an organic compound which is immiscible in water so as to move the fluorine-containing surfactant from the first aqueous phase to the first organic phase, and thereby obtaining an aqueous phase having a lowered concentration of the fluorine-containing surfactant as a second aqueous phase (i.e. a raffinate) and an organic phase including the moved fluorine-containing surfactant as
  • the fluorine-containing surfactant is moved to the second organic phase from the first aqueous phase.
  • the first pH value is relatively low, and generally in the acidic range, for example less than about 5 and preferably not greater than about 3.
  • This process of the first embodiment of the present invention can also be understood as a process for purifying the aqueous phase by separating the fluorine- containing surfactant or as a process for producing an aqueous phase in which the concentration of the fluorine-containing surfactant is reduced.
  • the first organic phase may be composed of an organic compound.
  • process water or waste water
  • the first aqueous phase may or may not also include polymer particles.
  • the polymer particles are those generated through the emulsion polymerization process which do not flocculate.
  • Such polymer particles can be understood as suspended solid content or as a substance which may convert to the suspended solid content.
  • the polymer particles can be made of a fluoropolymer. The fluoropolymer is obtained from at least one monomer which contains fluorine.
  • the fluoropolymer can be obtained from, for example, at least one monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, and perfluoro(alkyl vinyl ether).
  • fluoropolymer examples include polytetrafluoroethylene, poly(vinylidene fluoride), tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro(propyl vinyl ether) copolymer, tetrafluoroethylene- vinylidene fluoride copolymer, and tetrafluoroethylene-hexafluoropropylene- perfluoro(alkyl vinyl ether) terpolymer.
  • the fluoropolymer may be obtained from at least one monomer which contains fluorine and another monomer(s) which does not contain fluorine, such as ethylene or propylene.
  • the first aqueous phase further includes the polymer particles, and the polymer particles are kept in the first aqueous phase when the first aqueous phase is contacted with the first organic phase so that the particles are contained in the second aqueous phase.
  • the second organic phase obtained includes the fluorine-containing surfactant and is substantially free of polymer particles.
  • the first aqueous phase further includes the polymer particles, and the polymer particles are moved to the first organic phase when the first aqueous phase is contacted with the first organic phase so that the particles are contained in the second organic phase.
  • the second aqueous phase can be discharged to the external environment without any additional treatment since the second aqueous phase includes reduced and preferably no fluorine-containing surfactant or polymer particles.
  • Whether the polymer particles are kept in the aqueous phase or move from the aqueous phase to the organic phase depends on various conditions such as the combination of the surfactant, the polymer particles and the organic compound selected to be the organic phase, the relation of the specific gravities of the organic compound, the polymer particles and water, as well as the pH value of the aqueous phase.
  • a process for separating a fluorine-containing surfactant from a third organic phase wherein the third organic phase includes the fluorine-containing surfactant and an organic compound which is immiscible in water, the process comprising: contacting the third organic phase with a third aqueous phase including water so as to move the fluorine-containing surfactant from the third organic phase to the third aqueous phase, thereby obtaining an organic phase having a lowered concentration of the fluorine-containing surfactant as a fourth organic phase and an aqueous phase containing the moved fluorine-containing surfactant as a fourth aqueous phase, and the third aqueous phase having a second pH value when it is contacted with the third organic phase.
  • the fluorine- containing surfactant is moved to the fourth aqueous phase from the third organic phase.
  • the second pH value is relatively high, and generally in the range from around neutral to alkaline, for example greater than about 5 and preferably not less than about 8. By selecting the second pH value in this range, the extraction of the fluorine-containing surfactant occurs effectively from the organic phase to the aqueous phase.
  • This process of the fourth embodiment of the present invention can also be understood as a process for purifying the organic phase by separating the fluorine- containing surfactant or as a process for producing an organic phase in which content of the fluorine-containing surfactant is reduced.
  • the fourth organic phase obtained by this process can be used as the first organic phase of the first embodiment of the present invention.
  • the third aqueous phase may be composed of water.
  • the third organic phase may or may not further include polymer particles.
  • a fifth embodiment of the present invention there is provided a process wherein the processes of the first and the second embodiment of the present invention are conducted in combination so that the third organic phase corresponds to the second organic phase.
  • This process is also referred to as a two-step process of positive extraction and back extraction. According to this process of the fifth embodiment of the present invention, it becomes possible to recover the fluorine-containing surfactant from the first aqueous phase to the fourth aqueous phase.
  • This process may further include using the fourth organic phase as the first organic phase.
  • the organic phase obtained after the back extraction can be reused in the positive extraction for recycling.
  • the first aqueous phase includes polymer particles and they move to the second organic phase
  • the third organic phase contains the polymer particles, and they are contained in the forth organic phase. According to this case, it is possible to divide the fluorine-containing surfactant and the polymer particles into different phases.
  • the obtained fourth organic phase includes the fluorine-containing surfactant and substantially no polymer particles.
  • the organic phase is mainly composed of at least one organic compound.
  • the organic compound (or a mixture of the organic compounds when the organic phase includes two or more organic compounds) is such a fluid that when it is contacted with water, they separate into two phases in an acceptable degree.
  • the organic phase and the aqueous phase are contacted by, for example, stirring, mixing or shaking, and then the mixture of these phases is allowed to settle, two phases form by phase separation.
  • the organic compound to be used is substantially insoluble in or slightly soluble in water.
  • the solubility of the organic compound into water is not greater than about 10 g/L
  • organic compound having such solubility examples include acyclic or cyclic alkanes, ethers, esters, chlorinated and/or fluorinated compounds thereof and fluorinated amines.
  • suitable organic compounds include acyclic or cyclic alkanes, ethers, esters, chlorinated and/or fluorinated compounds thereof and fluorinated amines.
  • the present invention is not limited to organic compounds that are substantially insoluble or only slightly soluble in water. Organic compounds that are somewhat soluble (or disperse) in water can be used.
  • An acceptable solubility of the organic compound into water is not greater than about 100 g/L (about 10% by weight), and preferably not greater than about 10 g/L (about 1% by weight) at a temperature of 25°C.
  • organic compounds include alcohols such as n-butanol, carboxylic esters having a low molecular weight such as ethyl acetate and so on.
  • the fluorine-containing surfactant can be a fluorine-containing compound which has not more than about 38 carbon atoms per molecule. The invention is suitably employed for separating fluorine-containing anionic surfactants.
  • the fluorine-containing compound may be at least one selected from the group consisting of an anionic compound which does not contain an ether oxygen atom and is expressed by the following general formula (1): Y-(CF 2 ) xl -(CH 2 ) yl -A (1) (wherein Y is H or F, xl is an integer from 4 to 13, yl is an integer from 0 to 3, A is - SO 3 M or -COOM, and M is H, NR,, Li, Na or K), and an anionic compound which contains an ether oxygen atom and is expressed by the following general formula (2): F-(CF 2 ) x2 O(CFXCF 2 O) y2 -CFX-A (2)
  • the fluorine-containing surfactant is preferably perfluorooctanoic acid (PFO A) or the ammonium or sodium salt thereof.
  • PFO A perfluorooctanoic acid
  • the above described fluorine-containing surfactants can be present in the first aqueous phase at concentrations of from about 10 ppm to about 1 wt%, preferably from about 100 ppm to about 0.5 wt%.
  • the contacting of the aqueous phase and the organic phase can be carried out by mixing the aqueous phase and the organic phase and settling thereafter in a batch-wise mode.
  • this contacting can be carried out continuously.
  • the specific gravity of the organic compound (or a mixture of the organic compounds when the organic phase include two or more organic compounds) is preferably different from that of water by about 10% or more, and more preferably about 20% or from the specific gravity of water.
  • the continuous contacting can be conducted in a counter-current mode or in a co-current mode.
  • the process of the present invention described above can be conducted by using any appropriate apparatus which is suitable for extraction, such as a mixer settler, an extraction tower or a column. Conditions of the extraction including the extraction temperature, the ratio of the organic phase and the aqueous phase (S/F) can be selected set so as to accomplish the purpose of the present invention.
  • a process for recovering fluorine-containing surfactant comprising: conducting the process according to the first embodiment of the present invention, and subjecting the obtained second organic phase to distillation so that the fluorine-containing surfactant is recovered from the second organic phase while the rest is distilled off.
  • the fluorine-containing surfactant is readily recovered as a surfactant concentrated organic phase since the organic compound(s) in the organic phase is distilled off and removed.
  • the organic compound(s) preferably has a boiling point of about 10 to 120°C, and more preferably about 20 to 80°C. It is especially preferable to use organic compound(s) having a lower boiling point and a lower latent heat of vaporization than those of water in view of lower energy required for the distillation and also in view of processing costs and procedures. Conditions of the operation can be appropriately selected to concentrate the surfactant effectively.
  • the first aqueous phase includes polymer particles, it is preferable that the polymer particles are kept in the aqueous phase so as to recover the fluorine-containing surfactant separate from the polymer particles.
  • a process for recovering a fluorine-containing surfactant comprises: conducting the process according to the third embodiment or the fourth embodiment of the present invention, and subjecting the obtained fourth aqueous phase to a separation operation using a membrane or an ion exchange resin so that the fluorine-containing surfactant is recovered from the fourth aqueous phase as a surfactant concentrated aqueous phase.
  • the fluorine-containing surfactant is readily recovered as the surfactant concentrated aqueous phase since water in the aqueous phase passes through the membrane or the ion exchange resin and is thereby removed.
  • a kind of the membrane to be used and conditions of the operation can be appropriately selected to concentrate the surfactant effectively.
  • a reverse osmosis (RO) membrane is used in an appropriate way. Details of such operation using the membrane are described in Japanese Patent Kokai Publication No. 2002-58966 and WO 2002/01 3953, the entire contents of which are hereby incorporated by reference.
  • the type of ion exchange resin to be used and conditions of the operation e.g. flow rate
  • Details of operations using the ion exchange resin are described in Japanese Patent Kokai Publication No.
  • the overall process according to the present invention which may include the distillation, the membrane filtration or the ion exchange resin adsorption can be carried out in a batch-wise mode or in a continuous mode.
  • a process for separating a fluorine-containing surfactant from a first aqueous phase wherein the first aqueous phase includes the fluorine-containing surfactant and water
  • the process comprising: contacting the first aqueous phase with a first organic phase comprising at least one alcohol which is not completely soluble in water so as to move the fluorine- containing surfactant from the first aqueous phase to the first organic phase, thereby obtaining an aqueous phase having a lowered concentration of the fluorine-containing surfactant as a second aqueous phase and an organic phase including the moved fluorine-containing surfactant as a second organic phase.
  • Preferred alcohols for this embodiment are C4 (excluding tertiary butyl alcohol) alcohols to C6 alcohols, that is the isomers of butanol, except for tertiary butyl alcohol, the isomers of amyl (pentyl) alcohol, and the isomers of hexyl alcohol, more preferably n-butyl and n-amyl alcohols, still more preferably n-butyl alcohol.
  • the lower molecular weight alcohols separate from the aqueous phase more rapidly than do higher molecular weight alcohols. The latter have the advantage of being less soluble in the aqueous phase. Blends of alcohols may be used.
  • the process of the present invention can be applied, but not limited to, to separate and/or recover the fluorine containing surfactant such as perfluorooctanoic acid
  • PFOA fluoropolymer
  • Example 1 Twenty grams of perfluorohexane as an extraction solvent (an organic phase) and twenty grams of a solution of 100 ppm ammonium perfluorooctanoate in water as an extraction feed (an aqueous phase) were charged into a glass vessel and shaken up well. After settling for 15 hours, two phases were obtained by phase separation and the aqueous phase was analyzed using liquid chromatography to measure the concentration of ammonium perfluorooctanoate so as to confirm the extraction. A second experiment was conducted in the same manner, except that O.lg of concentrated sulfuric acid was added to the aqueous phase beforehand to make the aqueous phase acidic. The results are shown in Table 1.
  • Example 2 Experiments were conducted in the same manner as those in Example 1, except that the extraction solvent was 1-chloro-l, 1,2,2,3, 3, 4,4-octafluorobutane. The results are shown in Table 2. Table 2 Concentration of Ammonium Perfluorooctanoate in Aqueous Phase before and after Extraction
  • Example 4 Experiments were conducted in the same manner as those in Example 3, expect that the extraction feed was process water which was obtained from a polymerization fluid of tetrafluoroethylene homopolymer and the pH value of which was adjusted to 1.5.
  • the process water contained 118 ppm PFOA and 1000 ppm polymer particles. The results are shown in Table 4. Table 4
  • the organic compound is perfluorohexane, 1,1-dichloro-l- fluoroethane, chlorotrifluoroethylene dimer, or dichlorooctafluorobutane
  • the polymer particles are kept in the aqueous phase irrespective of the pH value of the aqueous phase.
  • the organic compound is 1-chloro-l, 1,2,2,3, 3,4,4- octafluorobutane or l,l,2,2-tetrafluoro-l-(2,2,2-trifluoroethoxy)ethane both of which have a greater specific gravity than water
  • the polymer particles are moved to and dispersed in the organic phase when the pH value of the aqueous phase before the extraction is in the acidic range, while the polymer particles are kept in the aqueous phase when the aqueous phase is about neutral.
  • Example 5 An experiment was conducted in the same manner as those in Example 3, except that the extraction solvent was ethyl acetate, and the extraction feed was a solution of
  • Example 1 An experiment was conducted in the same manner as those in Example 3, except that the extraction solvent was hexane, and the extraction feed was a solution of 100 ppm ammonium perfluorooctanoate in water of which pH value was adjusted to 1.5.
  • the extraction ratio was 17%.
  • Example 6 An experiment was conducted in the same manner as those in Example 3, except that the extraction solvent was dichlorooctafluorobutane, and the extraction feed was a solution of 100 ppm ammonium perfluorooctanoate in water of which pH value was adjusted in the range 1.5 to 4.1. The results are shown in Fig. 1. As understood from Fig. 1, the extraction occurred effectively especially when the pH was not greater than 2.0
  • Example 7 An experiment was conducted in the same manner as those in Example 3, except that the extraction solvent was dichlorooctafluorobutane, and the extraction feed was a solution of 100 ppm ammonium perfluorooctanoate in water of which pH value was adjusted to 1.5. A portion of the resulting organic phase of dichlorooctafluorobutane containing perfluorooctanoic acid and the same amount of a solution of IN NaOH were shaken up as in Example 3. Then, the resulting aqueous phase was analyzed, and it was found that ammonium perfluorooctanoate was extracted into the aqueous phase from the organic phase at an extraction rate of 95%.
  • the extraction solvent was dichlorooctafluorobutane
  • the extraction feed was a solution of 100 ppm ammonium perfluorooctanoate in water of which pH value was adjusted to 1.5.
  • Example 8 An amount of wastewater (an extraction feed) which was obtained after flocculation in a process of emulsion polymerization for producing PTFE and contained 52.4 ppm ammonium perfluorooctanoate and of which pH value was adjusted to 1.5, and the same quantity of one of three extraction solvents (perfluorohexane, dichlorooctafluorobutane and 1,1-dichloro-l-fluoroethane) were charged into a conical flask and shaken up several times.
  • three extraction solvents perfluorohexane, dichlorooctafluorobutane and 1,1-dichloro-l-fluoroethane
  • the amount of the extraction feed and the extraction solvent was: 50g for the case of perfluorohexane; lOOg for the case of dichlorooctafluorobutane; and lOOg for the case of 1,1-dichloro-l-fluoroethane.
  • the concentration of PFOA in the obtained aqueous phase was measured by HPLC to obtain an extraction ratio based on the concentration of PFOA in the extraction feed.
  • Table 5 Furthermore, both of the phases obtained at phase separation were separated from each other and filted respectively through a filter having a pore diameter of 0.1 ⁇ m. Thus resulting filter with solids content was weighed after having been heated at 120°C for 2 hours.
  • Example 8 demonstrates that almost no solid content was transferred from the aqueous phase to the organic phase in these cases.
  • Example 9 In this Example, n-butanol is used as the organic phase.
  • the aqueous phase is typical of the undiluted supernatant liquid obtained when the dispersion product of PTFE polymerization is concentrated, as disclosed in U.S. Patent No. 3,037,953.
  • Example 10 is repeated with an aqueous phase containing 1 wt % Triton® X-100, 5000 ppm fluorine-containing surfactant, and 5000 ppm polymer particles. Extractions are made with various ratios of aqueous to organic phase, using n-butanol as the organic phase. Analysis of the solids distribution between the organic and aqueous phase gives results similar to the ratios found in Example 9.

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  • Chemical Kinetics & Catalysis (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

L'invention concerne un procédé de séparation de tensioactif contenant du fluor par contact entre la première phase aqueuse renfermant ledit tensioactif et de l'eau et ayant un premier pH avec la première phase organique renfermant un composé organique non miscible avec l'eau, de manière à déplacer ledit tensioactif de la première phase aqueuse vers la première phase organique. Ainsi, on établit la seconde phase aqueuse à concentration inférieure de tensioactif contenant du fluor et la seconde phase organique contenant ledit tensioactif déplacé.
PCT/US2004/043528 2003-12-30 2004-12-27 Procede de separation de tensioactif contenant du fluor WO2005065800A1 (fr)

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US60/532,918 2003-12-30

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7659333B2 (en) 2005-11-24 2010-02-09 3M Innovative Properties Company Fluorinated surfactants for use in making a fluoropolymer
US7671112B2 (en) 2005-07-15 2010-03-02 3M Innovative Properties Company Method of making fluoropolymer dispersion
US7728087B2 (en) 2005-12-23 2010-06-01 3M Innovative Properties Company Fluoropolymer dispersion and method for making the same
US7754795B2 (en) 2006-05-25 2010-07-13 3M Innovative Properties Company Coating composition
US7776946B2 (en) 2005-07-15 2010-08-17 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
US7838608B2 (en) 2005-12-21 2010-11-23 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US8404790B2 (en) 2005-07-15 2013-03-26 3M Innovative Properties Company Aqueous emulsion polymerization process for producing fluoropolymers
WO2015110516A1 (fr) * 2014-01-22 2015-07-30 Friedrich-Alexander-Universität Erlangen-Nürnberg Procédé et dispositif permettant la séparation d'hydrocarbures fluorés à partir d'une phase aqueuse
US9212693B2 (en) 2007-04-27 2015-12-15 3M Innovative Properties Company Fluoropolymer coated articles
CN110683709A (zh) * 2019-07-15 2020-01-14 衢州市鼎盛化工科技有限公司 一种含氟废水零排放的处理方法

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US3882153A (en) * 1969-09-12 1975-05-06 Kureha Chemical Ind Co Ltd Method for recovering fluorinated carboxylic acid
US4282162A (en) * 1979-02-02 1981-08-04 Hoechst Aktiengesellschaft Recovery of fluorinated emulsifying acids from basic anion exchangers
US4623487A (en) * 1985-03-14 1986-11-18 E. I. Du Pont De Nemours & Company Process for recovery of fluorosurfactants
US6642415B1 (en) * 1999-11-05 2003-11-04 3M Innovative Properties Company Method for recovering fluorinated emulsifiers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882153A (en) * 1969-09-12 1975-05-06 Kureha Chemical Ind Co Ltd Method for recovering fluorinated carboxylic acid
US4282162A (en) * 1979-02-02 1981-08-04 Hoechst Aktiengesellschaft Recovery of fluorinated emulsifying acids from basic anion exchangers
US4623487A (en) * 1985-03-14 1986-11-18 E. I. Du Pont De Nemours & Company Process for recovery of fluorosurfactants
US6642415B1 (en) * 1999-11-05 2003-11-04 3M Innovative Properties Company Method for recovering fluorinated emulsifiers

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7671112B2 (en) 2005-07-15 2010-03-02 3M Innovative Properties Company Method of making fluoropolymer dispersion
US7776946B2 (en) 2005-07-15 2010-08-17 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
US8404790B2 (en) 2005-07-15 2013-03-26 3M Innovative Properties Company Aqueous emulsion polymerization process for producing fluoropolymers
US7659333B2 (en) 2005-11-24 2010-02-09 3M Innovative Properties Company Fluorinated surfactants for use in making a fluoropolymer
US7838608B2 (en) 2005-12-21 2010-11-23 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US7728087B2 (en) 2005-12-23 2010-06-01 3M Innovative Properties Company Fluoropolymer dispersion and method for making the same
US7754795B2 (en) 2006-05-25 2010-07-13 3M Innovative Properties Company Coating composition
US9212693B2 (en) 2007-04-27 2015-12-15 3M Innovative Properties Company Fluoropolymer coated articles
WO2015110516A1 (fr) * 2014-01-22 2015-07-30 Friedrich-Alexander-Universität Erlangen-Nürnberg Procédé et dispositif permettant la séparation d'hydrocarbures fluorés à partir d'une phase aqueuse
CN110683709A (zh) * 2019-07-15 2020-01-14 衢州市鼎盛化工科技有限公司 一种含氟废水零排放的处理方法

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