WO2025224604A2 - Résines échangeuses d'ions fonctionnalisées par alkylphosphonium - Google Patents

Résines échangeuses d'ions fonctionnalisées par alkylphosphonium

Info

Publication number
WO2025224604A2
WO2025224604A2 PCT/IB2025/054160 IB2025054160W WO2025224604A2 WO 2025224604 A2 WO2025224604 A2 WO 2025224604A2 IB 2025054160 W IB2025054160 W IB 2025054160W WO 2025224604 A2 WO2025224604 A2 WO 2025224604A2
Authority
WO
WIPO (PCT)
Prior art keywords
ion exchange
exchange resin
water
functional groups
pfas
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/IB2025/054160
Other languages
English (en)
Other versions
WO2025224604A3 (fr
Inventor
Nicholas L. UNTIEDT
Jonathan M. RYSS
Sean M. Smith
Brian T. Mader
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of WO2025224604A2 publication Critical patent/WO2025224604A2/fr
Publication of WO2025224604A3 publication Critical patent/WO2025224604A3/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/10—Inorganic material
    • 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
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • 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
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

Definitions

  • Wastewater treatment can involve a variety of physical, chemical, and biological processes and is a common form of pollution control.
  • ion exchange resins comprising an insoluble matrix having functional groups bonded thereto, the functional groups comprising a quaternary alkylphosphonium salt represented by the formula:
  • X" is an anionic counterion
  • Ri, R 2 and R3 are independently acyclic hydrocarbon groups having a carbon chain length Of C4 tO C18.
  • systems for the removal of PFAS from water comprising: a vessel containing an ion exchange resin, the ion exchange resin comprising an insoluble matrix having functional groups bonded thereto, the functional groups comprising a quaternary alkylphosphonium salt represented by the formula:
  • X- is an anionic counterion
  • Ri, R 2 and R3 are independently acyclic hydrocarbon groups having a carbon chain length of C4 to Cis; an inlet for directing a flow of water into the vessel to thereby contact the ion exchange resin; and an outlet for directing a flow of water out of the vessel.
  • PFAS PFAS
  • ion exchange resin the ion exchange resin comprising an insoluble matrix having functional groups bonded thereto, the functional groups comprising a quaternary alkylphosphonium salt represented by the formula: - P(RIR 2 R3) + X- wherein
  • X- is an anionic counterion
  • Ri, R 2 and R3 are independently acyclic hydrocarbon groups having a carbon chain length Of C4 tO C18.
  • the term “fully saturated” refers to an organic group including only carbon-carbon single bonds; the term “partially saturated” refers to an organic group including at least one double or triple carbon-carbon bond;
  • PFAS refers to per- and polyfluoroalkyl substances , such as, for example perfluorooctanoic acid (“PFOA”), perfluorooctane sulfonic acid (“PFOS”), perfluoropropionic acid (“PFPA”), perfluorobutyric acid (“PFBA”), trifluoroacetic acid (“TFA”), and perfluorobutane sulfonic acid (“PFBS”);
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctane sulfonic acid
  • PFPA perfluoropropionic acid
  • PFBA perfluorobutyric acid
  • TFA trifluoroacetic acid
  • PFBS perfluorobutane sulf
  • FIG. 1 is schematic of a system including an alkylphosphonium-functionalized ion-exchange resin according to the present disclosure.
  • FIG. 2 shows PFPA isotherms of trialkyphosponium and trialkylammonium functionalized PS resins.
  • FIG. 3 shows TFA isotherms of trialkyphosponium and trialkylammonium functionalized PS resins.
  • PF AS per- and polyfluoroalkyl substances
  • PFAS materials including four or fewer carbon atoms (e.g., sodium pentafluoropropionic acid, trifluoroacetic acid, heptafluorobutyric acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid) are often more difficult to remove from aqueous solutions than longer- chain PFAS materials.
  • resins with a higher affinity for these small-chain compounds may provide advantages when compared to the currently available resins used for ion exchange wastewater treatment.
  • PS resins including ammonium groups are known and used to remove small-chain PFAS from wastewater streams, with tributyl ammonium functionalized PS being the most effective resin for short-chain PFAS removal. Synthesis of resins such as these is typically accomplished by displacement between an amine nucleophile and a chloromethylene group appended to the polystyrene polymer backbone.
  • phosphonium-functionalized PS resins wherein the phosphonium functional groups are comprised of acyclic alkyl chains greater than four carbons in length (e.g., trihexylphosphine, trioctylphosphine), provide materials with a higher PFAS affinity than that of the tributylammonium- functionalized resin.
  • ion exchange resins including an insoluble matrix having functional groups bonded thereto, where the functional groups comprise a quaternary alkylphosphonium salt represented by the formula:
  • Ri, R2 and R3 are independently acyclic hydrocarbon groups having a carbon chain length of C4 to Cis.
  • the acyclic hydrocarbon groups can be normal or branched.
  • the acyclic hydrocarbon groups may be fully saturated or partially saturated.
  • the acyclic hydrocarbon groups may be substituted or unsubstituted. Any of the hydrocarbon groups may optionally include a heteroatom (e.g., O, N, S) in the hydrocarbon chain.
  • Ri, R2 and R3 are the same.
  • Ri, R2 and R3 are independently acyclic hydrocarbon groups having a carbon chain length of G, to Cs.
  • the insoluble matrix is selected from the group consisting of a polymer, a gel, a clay, a diatomaceous earth, and combinations thereof.
  • the polymer comprises polystyrene.
  • the anionic counterion is selected from the group consisting of a halide (e.g., chloride, bromide, iodide), an inorganic and ionic oxide (e.g., sulfate, nitrate), an organic anion (e.g., acetate), and combinations thereof.
  • ion exchange resins may be useful in embodiments of the present disclosure.
  • Such ion exchange resins typically include an insoluble matrix, substrate, or support structure.
  • the support structure is in the form of small, spherical beads having an average diameter ranging from about 1 mm to about 2 mm.
  • the support structure is a polymeric substrate, where the surface of the polymeric substrate includes sites that trap and release ions.
  • the ion exchange resins useful in the present invention may be based on one or more polymeric materials which may or may not be crosslinked.
  • the substrates are based on styrene that has been crosslinked with a cross-linker such as divinyl benzene, for example.
  • Crosslinked polymeric substrates may also be porous, and a crosslinked substrate will tend to be hard and not malleable.
  • Polymeric substrates that are not crosslinked can be softer and more malleable than a crosslinked substrate and can have a gel-like consistency, depending on the material used.
  • the ion exchange resin can comprise a matrix material in the form of non- spherical particles.
  • the matrix can comprise a material that is more amorphous or gel-like such as silica gel, diatomaceous earth, clay, or the like.
  • the ion exchange resin of the present disclosure is a ‘difunctional’ resin comprising two or more different quaternary alkylphosphonium groups.
  • a single ion exchange resin may comprise the quaternary amine groups +P(C6HI 3 )3 and +P(CsHi7)3.
  • Ion exchange resins suitable for use in embodiments of the present disclosure may be prepared by the chemical modification of resins known to those of ordinary skill in the relevant arts.
  • a suitable ion exchange resin is prepared by the reaction of a chloromethylated styrene bead (or other electrophilic group-containing resin) with a tertiary phosphine such as, for example, trihexylphosphine or trioctlyphosphine in a polar aprotic solvent such as 1,4-dioxane.
  • the reaction of the tertiary phosphine and the chloromethylated styrene bead is represented by Scheme 1, where Ri, R2, and R3 are as previously described.
  • resins within the scope of the present disclosure can comprise matrix materials other than styrene.
  • suitable matrix materials include without limitation polymers, gels, clays, diatomaceous earth and combinations of two or more of the foregoing.
  • a suitable polymer matrix is polystyrene.
  • a suitable gel matrix is silica gel.
  • FIG. 1 schematically illustrates an ion exchange system 10 for the removal of PFAS from water, according to the present disclosure.
  • the system 10 includes a flow- through vessel 12 which can be provided in any of a variety of configurations.
  • the vessel 12 is cylindrical column having an ion exchange bed 14 comprised of ion exchange resin contained within the vessel 12.
  • the ion exchange resins within the bed 14 are those described herein.
  • An inlet 16 at a first end of the vessel 12 allows for the introduction of untreated water into the vessel 12.
  • the water is pumped into the vessel 12 through the inlet 16 and through the ion exchange bed 14.
  • PFAS and other contaminants in the water stream are removed from the water by the ion exchange mechanism provided by the resins in the ion exchange bed 14.
  • Treated water is directed out of the vessel 12 through an outlet valve 18 at the opposite end of the vessel from the inlet 16.
  • untreated water comprising PFAS is exposed to an ion exchange resin for a sufficient period of time to have the PFAS within the untreated water be adsorbed onto the resins in an ion exchange process that substitutes the PFAS for another anion such as chloride, for example.
  • Exposing the untreated water to the resins can be accomplished in any manner.
  • an ion exchange bed is provided within a vessel that includes in inlet valve and an outlet valve.
  • Untreated water is directed into the vessel through the inlet valve and through the ion exchange bed where PFAS are removed.
  • the thus treated water comprises a lowered level of PFAS and exits the vessel through the outlet valve.
  • the flow may be directed from the outlet valve to another treatment station for further reduction of PFAS or for removal or treatment to remove or neutralize other impurities.
  • an amount of untreated water can be placed within a vessel along with an adequate amount of ion exchange resin.
  • the amount of resin within the vessel is typically selected to provide adequate ion exchange capacity to adsorb an expected loading of PFAS.
  • the vessel can be shaken or the contents stirred or agitated in some manner so that the PFAS are adequately adsorbed onto the resins and the ion exchange process is completed.
  • the water and resin may then be separated (e.g., by centrifuging, filtering and/or decanting) to yield a volume of treated water.
  • Resin 1.0 g was placed in a 25 mL thick-walled flask with tributyllphosphine (1.0 g, 4.9 mmol) and 1,4-dioxane (5 mL, 58.57 mmol) and heated to 90°C for 48 h. The reaction was cooled to room temperature, filtered, washed with about 100 mL H 2 O followed by 100 mL MeOH, then dried in an oven at 90°C for two days. The material was characterized by IR.
  • Resin 1.0 g was placed in a 25 mL thick-walled flask with trihexylphosphine (1.30 g, 4.5 mmol) and 1,4-dioxane (5 mL, 58.57 mmol) and heated to 90°C for 48 h. The reaction was cooled to room temperature, filtered, washed with about 100 mL H 2 O followed by 100 mL MeOH, then dried in an oven at 90°C for two days. The material was characterized by IR.
  • Resin 1.0 g was placed in a 25 mL thick-walled flask with trioctylphosphine (1.70 g, 4.5 mmol) and 1,4-dioxane (5 mL, 58.57 mmol) and heated to 90°C for 48 h. The reaction was cooled to room temperature, filtered, washed with ⁇ 100 mL H 2 O followed by 100 mL MeOH, then dried in an oven at 90°C for 2 days. The material was characterized by IR.
  • Resin 1.0 g was placed in a 25 mL thick-walled flask with tricyclohexylphosphine (1.25 g, 4.5 mmol) and 1,4-dioxane (5 mL, 58.57 mmol) and heated to 90°C for 48 h. Reaction was cooled to room temperature, filtered, washed with ⁇ 100 mL H 2 O followed by 100 mL MeOH, then dried in an oven at 90°C for 2 days. The material was characterized by IR.
  • Resin (1.0 g) was placed in a 25 mL thick-walled flask with triphenylphosphine (1.17 g, 4.5 mmol) and 1,4-dioxane (5 mL, 58.57 mmol) and heated to 90°C for 48 h. Reaction was cooled to room temperature, filtered, washed with ⁇ 100 mL H 2 O followed by 100 mL MeOH, then dried in an oven at 90°C for 2 days. The material was characterized by IR. Comparative Example 1 (CE-1). Preparation of tributylammonium functionalized polystyrene resin.
  • Resin 1.0 g was placed in a 25 mL thick-walled flask with tributylamine (3.8 mL, 16 mmol) and 1,4-dioxane (5 mL, 58.57 mmol) and heated to 90°C for 48 h. Reaction was cooled to room temperature, filtered, washed with ⁇ 100 mL H2O followed by 100 mL MeOH, then dried in an oven at 90°C for 2 days. The material was characterized by IR.
  • a 1000 ppm TFA solution was made by dissolving sodium trifluoroacetate (1.20 g) in DI water (998.80 mL).
  • a concentrated synthetic ground water solution (120 ppm NaCl; 120 ppm Na2SC>4; 40 ppm NaNO,: and 900 ppm NaHC’0,) was made by dissolving the appropriate amount of each listed salt in DI water.
  • IL solutions of a given concentration of TFA were made by combining 500 mL of the synthetic ground water solution and the required amount of 1000 ppm TFA solution and then diluting to volume of IL with DI water. This provided experimental stock solutions used in the TFA isotherm studies.
  • a 1000 ppm PFPA solution was made by dissolving sodium pentafluoropropionate (1.14 g) in DI water (998.86 mL).
  • a concentrated synthetic ground water solution (120 ppm NaCl; 120 ppm Na2SC>4; 40 ppm NaNO’,: and 900 ppm NaHCO,) was made by dissolving the appropriate amount of each listed salt in DI water.
  • IL solutions of a given concentration of PFPA (2.5 ppm; 5 ppm; 10 ppm) were made by combining 500 mL of the synthetic ground water solution and the required amount of 1000 ppm PFPA solution and then diluting to volume of IL with DI water. This provided experimental stock solutions used in the PFPA isotherm studies.
  • Solvent A Water with 50 mM ammonium bicarbonate
  • “Ce” is the concentration in ppm of the analyte in solution at equilibrium as measured by LC-MS.
  • the slope of the line calculated for each resin is a measurement of the effectiveness of the resin to adsorb the given analyte (in this case PFPA).
  • the resulting data indicates the most effective material to be the trioctylphophonium-modified resin, which shows an almost fourfold increase when compared to the tributylammonium-modified resin.
  • the slope of the line calculated for each resin is a measurement of the effectiveness of the resin to adsorb the given analyte (in this case TFA).
  • TFA analyte

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

L'invention concerne des résines échangeuses d'ions comprenant une matrice insoluble comportant des groupes fonctionnels liés à celle-ci, les groupes fonctionnels comprenant un sel d'alkylphosphonium quaternaire représenté par la formule : - P(R1R2R3)+ X- dans laquelle X-est un contre-ion anionique; et R1, R2 et R3 sont indépendamment des groupes hydrocarbonés acycliques ayant une longueur de chaîne carbonée de C4 à C18. L'invention concerne également des systèmes d'élimination des PFAS de l'eau et des procédés d'élimination des PFAS de l'eau.
PCT/IB2025/054160 2024-04-23 2025-04-21 Résines échangeuses d'ions fonctionnalisées par alkylphosphonium Pending WO2025224604A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463637621P 2024-04-23 2024-04-23
US63/637,621 2024-04-23

Publications (2)

Publication Number Publication Date
WO2025224604A2 true WO2025224604A2 (fr) 2025-10-30
WO2025224604A3 WO2025224604A3 (fr) 2026-01-02

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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919126A (en) * 1973-08-23 1975-11-11 Dow Chemical Co Insoluble polyalkyl phosphonium salt resins having crosslinked backbone
US4944878A (en) * 1989-11-16 1990-07-31 Iowa State University Research Foundation, Inc. Decontamination of water using nitrate selective ion exchange resin
US5670550A (en) * 1995-06-07 1997-09-23 The Regents Of The University Of California Office Of Technology Transfer Ion exchange polymers for anion separations
CN101605728B (zh) * 2007-02-16 2013-07-24 3M创新有限公司 用于从水中去除含氟化合物的系统和方法
WO2022246143A1 (fr) * 2021-05-21 2022-11-24 The Regents Of The University Of Michigan Pâte de bois à fonction ionique et procédés associés pour le traitement de l'eau
US20250197736A1 (en) * 2023-12-18 2025-06-19 Ecolab Usa Inc. Use of selected resins for sulfate removal in hydrocarbon mediums

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