CA2334023C - Process for the recovery of fluorinated alkanoic acids from wastewater - Google Patents
Process for the recovery of fluorinated alkanoic acids from wastewater Download PDFInfo
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- CA2334023C CA2334023C CA002334023A CA2334023A CA2334023C CA 2334023 C CA2334023 C CA 2334023C CA 002334023 A CA002334023 A CA 002334023A CA 2334023 A CA2334023 A CA 2334023A CA 2334023 C CA2334023 C CA 2334023C
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- wastewater
- fluorinated
- acids
- anion
- exchange resin
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- 239000002253 acid Substances 0.000 title claims abstract description 28
- 239000002351 wastewater Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000007513 acids Chemical class 0.000 title claims abstract description 21
- 238000011084 recovery Methods 0.000 title claims abstract description 7
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 4
- 238000010828 elution Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000004811 fluoropolymer Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 abstract description 4
- 239000003093 cationic surfactant Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/19—Acids containing three or more carbon atoms
- C07C53/21—Acids containing three or more carbon atoms containing fluorine
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/547—Tensides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processing Of Solid Wastes (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a process for the recovery of fluorinated emulsifier acids from wastewater, which comprises stabilizing the solids which are finely dispersed in the wastewater by means of a nonionic or cationic surfactant or a surface-active substance having an analogous effect and subsequently binding the fluorinated emulsifier acids on an anion-exchange resin and eluting the fluorinated emulsifier acids from this.
Description
Description Process for the recovery of fluorinated alkanoic acids from wastewater In the polymerization of fluorinated monomers in aqueous dispersion, use is made of fluorinated alkanoic acids as emulsifiers since they have no telogenic properties. In particular, use is made of the salts, preferably the alkali metal or ammonium salts, of perfluorinated or partially fluorinated alkane-carboxylic acids or alkanesulfonic acids. These compounds are prepared by electrofluorination or by telomerization of fluorinated monomers, which is costly. There have therefore been many attempts to recover these valuable materials from wastewater.
US-A-S 442 097 discloses a process for the recovery of fluorinated carboxylic acids in usable form from contaminated starting materials. In this process, the fluorinated carboxylic acid is, if necessary, liberated from these materials in an aqueous medium using a sufficiently strong acid, the fluorinated carboxylic acid is reacted with a suitable alcohol and the ester formed is distilled off. The startiiig material can here be a polymerization liquor, in particular from an emulsion polymerization in which the fluoropolymer is prepared in the form of colloidal particles with the aid of relatively high amounts of emulsifier. This process has proven very useful, but requires a certain concentration of fluorinated carboxylic acid in the starting material.
DE-A-20 44 986 discloses a process for the recovery of perfluorocarboxylic acids from diLlute solution, in which the dilute solution of the perfluorocarboxylic acids is brought into adsorption contact with a weak base anion-exchange resin and the perfluorocarboxylic acid present in the solution is thereby adsorbed on the WO 99/'62830 PCT/EP99/03673
US-A-S 442 097 discloses a process for the recovery of fluorinated carboxylic acids in usable form from contaminated starting materials. In this process, the fluorinated carboxylic acid is, if necessary, liberated from these materials in an aqueous medium using a sufficiently strong acid, the fluorinated carboxylic acid is reacted with a suitable alcohol and the ester formed is distilled off. The startiiig material can here be a polymerization liquor, in particular from an emulsion polymerization in which the fluoropolymer is prepared in the form of colloidal particles with the aid of relatively high amounts of emulsifier. This process has proven very useful, but requires a certain concentration of fluorinated carboxylic acid in the starting material.
DE-A-20 44 986 discloses a process for the recovery of perfluorocarboxylic acids from diLlute solution, in which the dilute solution of the perfluorocarboxylic acids is brought into adsorption contact with a weak base anion-exchange resin and the perfluorocarboxylic acid present in the solution is thereby adsorbed on the WO 99/'62830 PCT/EP99/03673
- 2 -anion-exchange resin, the anion-exchange resin is eluted with an aqueous ammonia solution and the adsorbed perfluorocarboxylic acid is thus transferred into the eluant and the acid is finally isolated from the eluate. However, complete elution requires relatively large amounts of dilute ammonia solution and this process is also very time-consuming. These disadvantages are overcome by the process known from US-A-4 282 162 for the elution of fluorinated emulsifier acids adsorbed on basic anion exchangers, in which the elution of the adsorbed fluorinated emulsifier acid from the anion exchanger is carried out using a mixture of dilute mineral acid and an organic solvent. In this process, the iori-exchange resin is regenerated at the same time by use of the acid.
It has been found that this last-narned process presents problems in industrial practice when, in particular, the wastewater processed contains very fine solids which in the past were often not recognized or at least not recognized as causing a problem. In this case, the apparatuses containing the anion-exchange resin become clogged with these solids more or less quickly, which becomes noticeable as a result of increased flow resistance and reduced performance. The upstream filters or frits customarily used are ineffective here.
It has also been found that these difficulties are caused by the fine solids being trapped in relatively stable colloidal suspension by the emulsifier acids.
When these acids are then removed from the system by means of the anion-exchange resin, this relatively stable dispersion is destroyed and the solid is precipitated and clogs the ion-exchange resin. It was thus also found that the performance of the process known from US-A-4 282 162 can be considerably improved and also made suitable for wastewater containing fine solids if the dispersion of the solids in the wastewater is stabilized by addition of a nonionic or WO 99~/62830 PCT/EP99/03673
It has been found that this last-narned process presents problems in industrial practice when, in particular, the wastewater processed contains very fine solids which in the past were often not recognized or at least not recognized as causing a problem. In this case, the apparatuses containing the anion-exchange resin become clogged with these solids more or less quickly, which becomes noticeable as a result of increased flow resistance and reduced performance. The upstream filters or frits customarily used are ineffective here.
It has also been found that these difficulties are caused by the fine solids being trapped in relatively stable colloidal suspension by the emulsifier acids.
When these acids are then removed from the system by means of the anion-exchange resin, this relatively stable dispersion is destroyed and the solid is precipitated and clogs the ion-exchange resin. It was thus also found that the performance of the process known from US-A-4 282 162 can be considerably improved and also made suitable for wastewater containing fine solids if the dispersion of the solids in the wastewater is stabilized by addition of a nonionic or WO 99~/62830 PCT/EP99/03673
- 3 -cationic surface-active additive (surfactant) before the wastewater is brought into coritact with the anion exchanger. The nonionic or cationic surfactants are not bound by the anion exchanger.
The invention accordingly provides a process for the recovery of fluorinated emulsifier acids from wastewater, which comprises stabilizing the solids which are finely dispersed in the wastewater by means of a nonionic or cationic surfactant or a surface-active substance having an analogous effect and subsequently binding the fluorinated emulsifier acids to an anion-exchange resin and eluting the fluorinated emulsifier acids from this.
Wastewater suitable for treatment: is waste process water in which surface-active fluorinated alkanoic acids are present. The process is particularly suitable for wastewater from the polymerization of fluorinated monomers by the emulsion method, in which the fluorinated monomer is converted in the presence of a relatively high concentration of fluorinated emulsifier acid and with mild stirring into a finely divided polymer which is in finely dispersed, colloidal form and in which the latex obtained is coagulated, for example by intensive stirring, afte:r the desired solids concentration has been reached, so that the polymer precipitates as a fine powder.
It has been found that in the known work-up it is especially relatively low molecu:lar weight polymer material which causes difficulties; the adverse effect of these low molecular weight polymers becomes particularly noticeable when the polymerization process leads to a broad molecular weight distribution. In the case of such "difficult" wastewater too, the process of the invention displays its capabilities.
The invention accordingly provides a process for the recovery of fluorinated emulsifier acids from wastewater, which comprises stabilizing the solids which are finely dispersed in the wastewater by means of a nonionic or cationic surfactant or a surface-active substance having an analogous effect and subsequently binding the fluorinated emulsifier acids to an anion-exchange resin and eluting the fluorinated emulsifier acids from this.
Wastewater suitable for treatment: is waste process water in which surface-active fluorinated alkanoic acids are present. The process is particularly suitable for wastewater from the polymerization of fluorinated monomers by the emulsion method, in which the fluorinated monomer is converted in the presence of a relatively high concentration of fluorinated emulsifier acid and with mild stirring into a finely divided polymer which is in finely dispersed, colloidal form and in which the latex obtained is coagulated, for example by intensive stirring, afte:r the desired solids concentration has been reached, so that the polymer precipitates as a fine powder.
It has been found that in the known work-up it is especially relatively low molecu:lar weight polymer material which causes difficulties; the adverse effect of these low molecular weight polymers becomes particularly noticeable when the polymerization process leads to a broad molecular weight distribution. In the case of such "difficult" wastewater too, the process of the invention displays its capabilities.
-4-The removal of solids before the wastewater is brought into contact with the ion-exchange resin is also known (see published Canadian Patent Application No. 2,334,105).
However, this has the disadvantage of a high outlay in terms of apparatus for the solids removal and the amount of auxiliary chemicals to be added (for example milk of lime, aluminum salts, flocculants). Particularly at low solids concentrations, complete removal of the colloidal material requires relatively large amounts of chemicals which are removed again to only a limited extent in the solids removal.
In the process of the invention, the outlay in terms of apparatuses and chemicals is considerably reduced since the addition of small amounts of a preferably readily biodegradable surfactant is sufficient for stabilizing the colloids and ensures trouble-free operation of the ion exchanger.
The adsorption of the emulsifier acids onto ion-exchange resins can be carried out in a manner known per se. Suitable resins are, in particular, strong base anion-exchange resins as are obtainable, for example, under the trade names AMBERLITE IRA-402, AMBERJET
4200 (both Rohm & Haas), a PUROLITE A845 (Purolite GmbH) or a LEWATIT MP-500 (Bayer AG).
The adsorption can be carried out in a manner known per se, with the ion-exchange resins being located in customary apparatuses such as tubes or columns through which the wastewater flows.
The elution of the bound emulsifier acids is likewise carried out in a manner known per se, with preference being given to the method described in US-A-4 282 162.
However, this has the disadvantage of a high outlay in terms of apparatus for the solids removal and the amount of auxiliary chemicals to be added (for example milk of lime, aluminum salts, flocculants). Particularly at low solids concentrations, complete removal of the colloidal material requires relatively large amounts of chemicals which are removed again to only a limited extent in the solids removal.
In the process of the invention, the outlay in terms of apparatuses and chemicals is considerably reduced since the addition of small amounts of a preferably readily biodegradable surfactant is sufficient for stabilizing the colloids and ensures trouble-free operation of the ion exchanger.
The adsorption of the emulsifier acids onto ion-exchange resins can be carried out in a manner known per se. Suitable resins are, in particular, strong base anion-exchange resins as are obtainable, for example, under the trade names AMBERLITE IRA-402, AMBERJET
4200 (both Rohm & Haas), a PUROLITE A845 (Purolite GmbH) or a LEWATIT MP-500 (Bayer AG).
The adsorption can be carried out in a manner known per se, with the ion-exchange resins being located in customary apparatuses such as tubes or columns through which the wastewater flows.
The elution of the bound emulsifier acids is likewise carried out in a manner known per se, with preference being given to the method described in US-A-4 282 162.
- 5 -Methods suitable for isolating the emulsifier acids in the high purity required for use in polymerization are, for example, those described in the abovementioned US-A-5 442 097 or that described in US-A-5 312 935 in which the eluate is firstly substantially freed of water and then treated with oxidizir.ig agents.
The wastewater remaining after adsorption of the emulsifier acids is treated in a known manner, depending on the content of other materials.
The invention is illustrated by the following examples.
Examples 1 to 4 and comparative example The starting material used is wastewater from the copolymerization of tetrafluoroethylene and perfluoro(n-propyl vinyl ether) in which the ammonium salt of n- and iso-perfluorooctanoic acid (PFOA) is used as emulsifier. The PFOA concentration is 750 mg/l.
In a stirred vessel, 1000 g of this liquor are admixed with 0.1 g of the nonionic surfactant TRITON X-100 (Rohm & Haas, p-octylphenol ethoxylate, CAS No.
9002-93-1) or GENAPOL UD 088 (Hoechst AG, fatty alcohol polyglycol ether) and stirred.
About 50 ml of a commercial stronq base ion-exchange resin ( AMBERLITE IRA-402, Rohm & Haas; styrene-divinylbenzene type, anion: chloride, gel, total capacity: 1.3 eq/l, bulk density: 710 g/1) are placed in a cylindrical glass column (length: 25 cm, diameter:
16 mm) provided with a glass frit and rinsed with water. To load the ion exchanger, the solution is pumped upward through the bed by means of a pump. The water leaving the column is collected as a plurality of samples and the PFOA concentration is determined. The pressure drop over the ion exchanger bed is measured by means of,a manometer. The water leaving the column is
The wastewater remaining after adsorption of the emulsifier acids is treated in a known manner, depending on the content of other materials.
The invention is illustrated by the following examples.
Examples 1 to 4 and comparative example The starting material used is wastewater from the copolymerization of tetrafluoroethylene and perfluoro(n-propyl vinyl ether) in which the ammonium salt of n- and iso-perfluorooctanoic acid (PFOA) is used as emulsifier. The PFOA concentration is 750 mg/l.
In a stirred vessel, 1000 g of this liquor are admixed with 0.1 g of the nonionic surfactant TRITON X-100 (Rohm & Haas, p-octylphenol ethoxylate, CAS No.
9002-93-1) or GENAPOL UD 088 (Hoechst AG, fatty alcohol polyglycol ether) and stirred.
About 50 ml of a commercial stronq base ion-exchange resin ( AMBERLITE IRA-402, Rohm & Haas; styrene-divinylbenzene type, anion: chloride, gel, total capacity: 1.3 eq/l, bulk density: 710 g/1) are placed in a cylindrical glass column (length: 25 cm, diameter:
16 mm) provided with a glass frit and rinsed with water. To load the ion exchanger, the solution is pumped upward through the bed by means of a pump. The water leaving the column is collected as a plurality of samples and the PFOA concentration is determined. The pressure drop over the ion exchanger bed is measured by means of,a manometer. The water leaving the column is
- 6 -collected as a plurality of samples and the PFOA
concentration is determined.
The loading experiment without addition of surfactant (comparative example) had to be stopped since the pressure drop increased to above 1 bar/m as a result of precipitated polymer and the resin displayed significant conglutination.
Example 1 Example 2 Example 3 Example 4 Comparative Example Surfact-ant: GENAPOL TRITON TRITON TRITON none Amount of Concen- 100 mg/I 100 mg/I 200 mg/I 400 mg/1 wastewater ml tration Pressure drop over ion exchan er bed bar/m 0 0.12 0.24 0.24 0.16 = 0.20 200 0.16 0.20 0.24 0.16 0.40 300 0.12 0.24 0.24 0.24 400 0.12 0.24 0.24 1.60 (stopped) 500 0.12 0.24 0.24 600 0.12 0.24 0.24 1000 0.12 PFOA in the 2.5 5.1 4.2 4.2 3.3 wastewater m /I
Example 5 150 ml of an elution solution are mixed from methanol, concentrated sulfuric acid (96%) and water (proportions by mass: 89%, 7%, 4%). The ion exchanger column is, after loading, firstly rinsed with 100 ml of water in order to remove remaining wastewater from the column.
The elution solution is then passed through the column at a linear velocity of 0.5 m/h and is collected. The column is. finally rinsed with a further 50 ml of water.
The elution solution contains about 95% of the emulsifier solution in the wastewater used.
concentration is determined.
The loading experiment without addition of surfactant (comparative example) had to be stopped since the pressure drop increased to above 1 bar/m as a result of precipitated polymer and the resin displayed significant conglutination.
Example 1 Example 2 Example 3 Example 4 Comparative Example Surfact-ant: GENAPOL TRITON TRITON TRITON none Amount of Concen- 100 mg/I 100 mg/I 200 mg/I 400 mg/1 wastewater ml tration Pressure drop over ion exchan er bed bar/m 0 0.12 0.24 0.24 0.16 = 0.20 200 0.16 0.20 0.24 0.16 0.40 300 0.12 0.24 0.24 0.24 400 0.12 0.24 0.24 1.60 (stopped) 500 0.12 0.24 0.24 600 0.12 0.24 0.24 1000 0.12 PFOA in the 2.5 5.1 4.2 4.2 3.3 wastewater m /I
Example 5 150 ml of an elution solution are mixed from methanol, concentrated sulfuric acid (96%) and water (proportions by mass: 89%, 7%, 4%). The ion exchanger column is, after loading, firstly rinsed with 100 ml of water in order to remove remaining wastewater from the column.
The elution solution is then passed through the column at a linear velocity of 0.5 m/h and is collected. The column is. finally rinsed with a further 50 ml of water.
The elution solution contains about 95% of the emulsifier solution in the wastewater used.
Claims (5)
1. A process for the recovery of fluorinated emulsifier acids from wastewater, which comprises stabilizing low molecular weight fluoropolymer solids which are finely dispersed in the wastewater by means of a surfactant or a surface-active substance and subsequently binding the fluorinated emulsifier acids to an anion-exchange resin and eluting the fluorinated emulsifier acids from this.
2. The process as claimed in claim 1, wherein wastewater from the polymerization of fluorinated monomers is used.
3. The process as claimed in claim 1 or 2, wherein material which can be converted into the solids is precipitated.
4. The process as claimed in any one of claims 1 to 3, wherein the anion-exchange resin used is a strong base anion-exchange resin.
5. The process as claimed in any one of claims 1 to 4, wherein elution is carried out using a mixture of dilute mineral acid and an organic solvent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19824615.3 | 1998-06-02 | ||
| DE19824615A DE19824615A1 (en) | 1998-06-02 | 1998-06-02 | Process for the recovery of fluorinated alkanoic acids from waste water |
| PCT/EP1999/003673 WO1999062830A1 (en) | 1998-06-02 | 1999-05-27 | Method for recovering fluorinated alkanoic acids from waste waters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2334023A1 CA2334023A1 (en) | 1999-12-09 |
| CA2334023C true CA2334023C (en) | 2007-12-04 |
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ID=7869668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CA002334023A Expired - Fee Related CA2334023C (en) | 1998-06-02 | 1999-05-27 | Process for the recovery of fluorinated alkanoic acids from wastewater |
Country Status (17)
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| US (1) | US6518442B1 (en) |
| EP (2) | EP1209125B2 (en) |
| JP (1) | JP3678650B2 (en) |
| KR (1) | KR100499439B1 (en) |
| CN (1) | CN1191997C (en) |
| AT (2) | ATE228972T1 (en) |
| AU (1) | AU4370299A (en) |
| CA (1) | CA2334023C (en) |
| CZ (1) | CZ20004380A3 (en) |
| DE (3) | DE19824615A1 (en) |
| ES (1) | ES2176138T3 (en) |
| HU (1) | HUP0102254A3 (en) |
| PL (1) | PL194343B1 (en) |
| RU (1) | RU2224721C2 (en) |
| TR (1) | TR200003531T2 (en) |
| WO (1) | WO1999062830A1 (en) |
| ZA (1) | ZA200006906B (en) |
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| US20030125421A1 (en) * | 2001-08-03 | 2003-07-03 | Hermann Bladel | Aqueous dispersions of fluoropolymers |
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| CN100381366C (en) * | 2002-06-19 | 2008-04-16 | 笹仓机械工程有限公司 | Method for recovering fluorine-containing emulsifier |
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| US20060135681A1 (en) | 2004-12-22 | 2006-06-22 | Cavanaugh Robert J | Viscosity control for reduced fluorosurfactant aqueous fluoropolymer dispersions by the addition of cationic surfactant |
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| US20080264864A1 (en) * | 2007-04-27 | 2008-10-30 | 3M Innovative Properties Company | PROCESS FOR REMOVING FLUORINATED EMULSIFIER FROM FLUOROPOLMER DISPERSIONS USING AN ANION-EXCHANGE RESIN AND A pH-DEPENDENT SURFACTANT AND FLUOROPOLYMER DISPERSIONS CONTAINING A pH-DEPENDENT SURFACTANT |
| GB0712191D0 (en) * | 2007-06-25 | 2007-08-01 | 3M Innovative Properties Co | Process for removing fluorinated compounds for an aqueous phase originating from the preparation of fluoropolymers |
| JP5256002B2 (en) * | 2008-11-25 | 2013-08-07 | オルガノ株式会社 | Wastewater treatment system for photoresist development wastewater |
| JP5983615B2 (en) * | 2011-09-13 | 2016-09-06 | 旭硝子株式会社 | Method for recovering anionic fluorine-containing emulsifier |
| EP3056275B1 (en) | 2013-10-10 | 2020-04-29 | AGC Inc. | Method for recovering fluorinated emulsifier |
| DE102014100694A1 (en) | 2014-01-22 | 2015-07-23 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Process and apparatus for separating fluorinated hydrocarbons from an aqueous phase |
| EP3127602B1 (en) * | 2014-03-31 | 2018-12-19 | AGC Inc. | Recovery method for anionic fluorine-containing emulsifier |
| JP6991994B2 (en) | 2016-11-15 | 2022-02-03 | 東洋鋼鈑株式会社 | Method for manufacturing polyester-based thermoplastic film, method for inspecting polyester-based thermoplastic film, polyester-based thermoplastic film or its resin material |
| US11548800B2 (en) | 2019-04-26 | 2023-01-10 | Geyser Remediation LLC | Water purification apparatus and method |
| CN113728015A (en) * | 2019-04-26 | 2021-11-30 | 大金工业株式会社 | Method for producing aqueous fluoropolymer dispersion and aqueous fluoropolymer dispersion |
| US11452987B2 (en) | 2019-06-19 | 2022-09-27 | The Johns Hopkins University | Contaminate sequestering coatings and methods of using the same |
| CA3144040A1 (en) * | 2019-06-26 | 2020-12-30 | Chromafora Ab | A process for removal of pfas from water |
| US20220306491A1 (en) | 2019-06-28 | 2022-09-29 | Katholieke Universiteit Leuven | Adsorptive Removal of Perfluorinated or Partially Fluorinated Surfactants |
| TWI727723B (en) * | 2020-03-26 | 2021-05-11 | 臺北醫學大學 | Method for treating and recycling fluorine-containing waste solvent |
| US11840471B1 (en) | 2021-12-20 | 2023-12-12 | Republic Services, Inc. | Method for removing per- and polyfluoroalkyl substances (PFAS) from waste water |
| WO2023208919A1 (en) | 2022-04-28 | 2023-11-02 | Röhm Gmbh | Poly(meth)acrylat impact modifier with reduced metal ion content and method for its production |
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| US3536643A (en) † | 1967-09-01 | 1970-10-27 | Cosden Oil & Chem Co | Polyethylene emulsion process |
| US3882153A (en) † | 1969-09-12 | 1975-05-06 | Kureha Chemical Ind Co Ltd | Method for recovering fluorinated carboxylic acid |
| GB1314607A (en) | 1969-09-12 | 1973-04-26 | Kureha Chemical Ind Co Ltd | Method for recovering perfluorinated emulsifiers |
| DE2903981A1 (en) * | 1979-02-02 | 1980-08-07 | Hoechst Ag | RECOVERY OF FLUORINATED EMULGATOR ACIDS FROM BASIC ANION EXCHANGERS |
| DE2908001C2 (en) † | 1979-03-01 | 1981-02-19 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of concentrated dispersions of fluoropolymers |
| DE4213154C1 (en) | 1992-04-22 | 1993-06-17 | Hoechst Ag, 6230 Frankfurt, De | |
| DE4402694A1 (en) | 1993-06-02 | 1995-08-03 | Hoechst Ag | Process for the recovery of fluorinated carboxylic acids |
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1998
- 1998-06-02 DE DE19824615A patent/DE19824615A1/en not_active Withdrawn
-
1999
- 1999-05-27 EP EP02075014.7A patent/EP1209125B2/en not_active Expired - Lifetime
- 1999-05-27 CZ CZ20004380A patent/CZ20004380A3/en unknown
- 1999-05-27 JP JP2000552048A patent/JP3678650B2/en not_active Expired - Fee Related
- 1999-05-27 AT AT99926443T patent/ATE228972T1/en not_active IP Right Cessation
- 1999-05-27 DE DE59903664T patent/DE59903664D1/en not_active Expired - Lifetime
- 1999-05-27 EP EP99926443A patent/EP1093441B1/en not_active Expired - Lifetime
- 1999-05-27 TR TR2000/03531T patent/TR200003531T2/en unknown
- 1999-05-27 AU AU43702/99A patent/AU4370299A/en not_active Abandoned
- 1999-05-27 CA CA002334023A patent/CA2334023C/en not_active Expired - Fee Related
- 1999-05-27 US US09/700,639 patent/US6518442B1/en not_active Expired - Lifetime
- 1999-05-27 CN CNB998068977A patent/CN1191997C/en not_active Expired - Lifetime
- 1999-05-27 DE DE59912370T patent/DE59912370D1/en not_active Expired - Lifetime
- 1999-05-27 RU RU2000133334/15A patent/RU2224721C2/en not_active IP Right Cessation
- 1999-05-27 HU HU0102254A patent/HUP0102254A3/en unknown
- 1999-05-27 AT AT02075014T patent/ATE301103T1/en not_active IP Right Cessation
- 1999-05-27 WO PCT/EP1999/003673 patent/WO1999062830A1/en active IP Right Grant
- 1999-05-27 PL PL99344575A patent/PL194343B1/en not_active IP Right Cessation
- 1999-05-27 KR KR10-2000-7013595A patent/KR100499439B1/en not_active IP Right Cessation
- 1999-05-27 ES ES99926443T patent/ES2176138T3/en not_active Expired - Lifetime
-
2000
- 2000-11-24 ZA ZA200006906A patent/ZA200006906B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP1209125A3 (en) | 2003-10-22 |
| PL344575A1 (en) | 2001-11-05 |
| US6518442B1 (en) | 2003-02-11 |
| ATE301103T1 (en) | 2005-08-15 |
| HUP0102254A3 (en) | 2002-06-28 |
| CA2334023A1 (en) | 1999-12-09 |
| TR200003531T2 (en) | 2001-04-20 |
| EP1093441A1 (en) | 2001-04-25 |
| DE19824615A1 (en) | 1999-12-09 |
| ATE228972T1 (en) | 2002-12-15 |
| PL194343B1 (en) | 2007-05-31 |
| ES2176138T1 (en) | 2002-12-01 |
| KR100499439B1 (en) | 2005-07-07 |
| EP1093441B1 (en) | 2002-12-04 |
| EP1209125B2 (en) | 2014-07-23 |
| ZA200006906B (en) | 2001-09-26 |
| DE59912370D1 (en) | 2005-09-08 |
| KR20010071370A (en) | 2001-07-28 |
| WO1999062830A1 (en) | 1999-12-09 |
| DE59903664D1 (en) | 2003-01-16 |
| CZ20004380A3 (en) | 2001-09-12 |
| HUP0102254A2 (en) | 2001-10-28 |
| EP1209125B1 (en) | 2005-08-03 |
| AU4370299A (en) | 1999-12-20 |
| JP3678650B2 (en) | 2005-08-03 |
| CN1303356A (en) | 2001-07-11 |
| JP2002516885A (en) | 2002-06-11 |
| RU2224721C2 (en) | 2004-02-27 |
| ES2176138T3 (en) | 2003-07-01 |
| CN1191997C (en) | 2005-03-09 |
| EP1209125A2 (en) | 2002-05-29 |
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