WO2026024681A1 - Destruction de substances polyfluoroalkylées à l'aide d'enzymes et de catalyseurs inorganiques - Google Patents

Destruction de substances polyfluoroalkylées à l'aide d'enzymes et de catalyseurs inorganiques

Info

Publication number
WO2026024681A1
WO2026024681A1 PCT/US2025/038591 US2025038591W WO2026024681A1 WO 2026024681 A1 WO2026024681 A1 WO 2026024681A1 US 2025038591 W US2025038591 W US 2025038591W WO 2026024681 A1 WO2026024681 A1 WO 2026024681A1
Authority
WO
WIPO (PCT)
Prior art keywords
enzyme
water
stream
inorganic catalyst
organofluorine compounds
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/US2025/038591
Other languages
English (en)
Other versions
WO2026024681A9 (fr
Inventor
Gary J. BROBERG
Hannah R. GIUSTI
Graham J. MACDONALD
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.)
Practical Applications Inc
Original Assignee
Practical Applications Inc
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 Practical Applications Inc filed Critical Practical Applications Inc
Publication of WO2026024681A1 publication Critical patent/WO2026024681A1/fr
Publication of WO2026024681A9 publication Critical patent/WO2026024681A9/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/16—Feed pretreatment
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/25—Recirculation, recycling or bypass, e.g. recirculation of concentrate into the feed
    • B01D2311/252—Recirculation of concentrate
    • B01D2311/2523—Recirculation of concentrate to feed side
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2696—Catalytic reactions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/18—Removal of treatment agents after treatment

Definitions

  • the present disclosure removes per-and polyfluoroalkyl substances (PF AS) from water using enzymes, and non-toxic metal catalysts.
  • PF AS per-and polyfluoroalkyl substances
  • PFAS substances were introduced into consumer products in the 1930s and at the time were believed to be non-toxic. These chemicals were known for their ability to be stable in the environment. Today PFAS substances are considered forever chemicals due to their inability to break-down in the environment. Recently these chemicals have been found to negatively affect living organisms at extremely low levels (less than 20 parts per trillion).
  • PFAS ingredients have been used in many consumer and commercial products including firefighting foams, fire retardants, water repellents, and as surfactants.
  • the present disclosure is directed to remove per-and polyfluoroalkyl substances (PFAS) from water.
  • PFAS per-and polyfluoroalkyl substances
  • the disclosure includes methods of using the catalyst to improve the reaction performance while minimizing the total catalyst mass needed for treatment.
  • the ratio of PFAS to enzyme may be 3 pg to 3,000,000 pg and the inorganic catalyst may be powdered platinum with a weight concentration in the reactor of 8 g platinum in 1,000 g water.
  • the unique attribute to the disclosure is it produces little to no residual. Sorption methods for removing PF AS include ion exchange and activated carbon. Both methods produce a significant residual that requires further treatment/destruction. This method produces between 0.1% to 1% waste, depending on the PFAS feed concentration.
  • a method is disclosed of removing organofluorine compounds from contaminated water comprising:
  • the disclosure provides A method of removing organofluorine compounds from contaminated water, the method comprising: a) mixing the contaminated water with an enzyme; b) passing the mixture through a catalytic reactor, the catalytic reactor comprising a scaffold comprising an inorganic catalyst selected from the group consisting of a metal, a metal cation, an organometallic compound, and combinations thereof; c) filtering the mixture passed through the catalytic reactor by ultrafiltration to obtain a permeate stream and a retentate stream, wherein the organofluorine compounds present in the permeate stream are reduced by at least 50 wt% compared to the amount present in the contaminated water; and d) recovering the enzyme from the retentate stream.
  • the disclosure provides a system for removing organofluorine compounds from a stream of water, the system comprising: (a) a water supply feed to provide the stream of water; (b) an injection device, downstream of the feed water supply mechanism, configured to deliver enzyme into the stream of water; (c) a catalytic reactor, having an inorganic catalyst disposed therein, downstream of the injection device, configured to receive the stream of water so that the stream of water mixes with the inorganic catalyst; (d) an ultrafiltration device, configured to receive an output of the catalytic reactor, having an ultrafiltration membrane, the ultrafiltration membrane configured to separate the enzyme and any organofluorine compounds bound to the enzyme from the water stream, so as to produce (i) a permeate stream in which the organofluorine compounds arc reduced at least 50 wt% compared to the amount present in the stream of water, and (ii) a retentate stream comprising free enzyme and enzyme bound to the organofluorine compounds; and (e)
  • the organofluorine compounds include polyfluoroalkyl substances and/or perfluoroalkyl substances.
  • the enzyme is chosen from the group consisting of amylase, glutathione-S-transferase, alanine transaminase, aspartate transaminase, and combinations thereof. In some such embodiments, the enzyme is a food-grade amylase.
  • the inorganic catalyst is a metal. In some such embodiments, the metal is selected from the group consisting of Fe, Mg, Cr, Ti, Mn, Au, Ag, Pt, and combinations thereof. In some such embodiments, the metal is Pt.
  • the metal is prepared to have a high surface area.
  • the method is performed at a temperature between 1 and 99 degrees Celsius.
  • compositions comprising an inorganic catalyst and a enzyme, the composition having efficacy for removing organofluorine compounds from water.
  • the enzyme is an amylase.
  • the organofluorine compounds include compounds selected from the group consisting of perfluoroalkyl substances, polyfluoroalkyl substances, and combinations thereof.
  • the inorganic catalyst is a metal selected from the group consisting of Fe, Mg, Cr, Ti, Mn, Au, Ag, Pt, and combinations thereof. In a specific composition, the metal is Pt.
  • a reactor design that allows the enzyme and catalyst to capitalize on using proximity as a means of accelerating reactions by developing organic scaffolds that colocate a catalyst and starting material.
  • the generic structure of a scaffolding catalyst has a catalyst-binding site (or bound catalytic residue) and a substrate-binding site.
  • the key insight for this concept is that substrate binding does not require simultaneous activation of a functional group; therefore, the scaffolds can be applied potentially to a wide range of transformations to significantly accelerate the reaction rates.
  • FIG. 1 is a schematic showing operation of a PFAS treatment system, according to an aspect of the present disclosure.
  • Fig. 1 shows an embodiment of the present disclosure for removing polyfluoroalkyl substances (PFAS) from water.
  • PFAS polyfluoroalkyl substances
  • Water samples containing PFAS are treated using a enzyme in the presence of a non-toxic metal catalyst.
  • Water samples with concentrations of PFAS from 3 parts per trillion (ppt) to 5,000 parts per trillion (ppt) were treated.
  • Ultrafilter permeate stream treatment removal performance is 99% PFAS removed or higher.
  • Available enzymes that can be employed for treatment include but are not limited to amylase, glutathione-S-transferase, alanine transaminase, aspartate transaminase, and enzymes containing amino acid combinations of aspartic acid, histidine, and lincomycin.
  • Available non-toxic metal catalysts that may be employed for treatment include iron, magnesium, chrome, titanium, manganese, gold, silver, and platinum.
  • water samples containing PFAS may be mixed with a enzyme and a non-toxic metal catalyst and fdtered via an ultrafilter.
  • Non-toxic metallic catalyst is prepared to have a high surface area.
  • PFAS compounds are both decomposed and chemically bound with the enzyme.
  • liquid is pumped to an ultrafilter where the permeate PFAS concentration is less than 1 % of the feed stream and the enzyme and other PFAS byproducts are recovered in the ultrafilter reject (retentate).
  • reject is 0.1 to 1% (wt.) of the feed stream mass. Treatment can be performed at temperatures from 1 degree Celsius to 99 degrees Celsius.
  • a process is designed for production of PFAS free water, by continuous or batch methods. Reagent and catalyst spatial distribution is used to increase the reaction kinetics performance. Typically, waters contaminated with PFAS have PFAS concentrations of 1 to 3000 parts per trillion. An excess dose of enzyme is used to improve the probability of contact with the PFAS compounds.
  • a reactor is designed to maximize available reaction sites for the PFAS-enzyme reaction, such as a fluidized bed reactor, powdered metals, or and the like.
  • a reactor system and process employing a non-toxic metal catalyst may be employed wherein the reactor system comprises a vertical reactor having a scaffolding medium permeable distribution plate towards the base thereof, a supply line to supply fluidizing medium consisting of water, contaminant, and well distributed enzyme to the base of the reactor, a non-toxic metal catalyst substrate through which fluidizing medium attaches, and a substrate recovery screen and/or disengagement zone to prevent substrate loss.
  • a water sample contaminated with PFAS (total PFAS concentration is 5 to 3000 ppt) is added to a 1,000 mL Erlenmeyer Flask.
  • Standard treatment conditions include 5 g of amylase, 8 g of powdered platinum, a four-hour retention time, and mixed at room temperature.
  • the mixture is pumped through an ultrafilter and the filtered water is analyzed for PFAS chemicals using EP A (Environmental Protection Agency) test method 537.1.
  • Different retention times for treatment include 24 hours, 8 hours, 4 hours, and 1 hour.
  • Table 2 includes data collected from each retention time variable. Remaining standard treatment conditions were constant. As time decreases, the amount of unregulated PFAS contaminants increases, indicating a correlation between time and treatment. In all treated samples, regulated contaminants are reported as non-detected. This observation indicates that while time has some impact, it is not a determining factor.
  • Fluorine Analysis was performed again using a sample with higher PF AS concentrations.
  • Raw water from Fort Devens Air Force Base was found to have 2717.5 ng/L of regulated PF AS contaminates, and 519.7 ng/L of unregulated PF AS contaminates.
  • a raw sample, permeate treated sample, and reject treated sample were sent for analysis.
  • Table 6 includes the analysis data. The raw sample was found to have 5.18 ug/L organic fluorine and both treated samples had no detection for organic fluorine.
  • a method of removing organo fluorine compounds from contaminated water comprising: a) mixing the contaminated water with an enzyme; b) passing the mixture through a catalytic reactor, the catalytic reactor comprising a scaffold comprising an inorganic catalyst selected from the group consisting of a metal, a metal cation, an organometallic compound, and combinations thereof; c) filtering the mixture passed through the catalytic reactor by ultrafiltration to obtain a permeate stream and a retentate stream, wherein the organofluorine compounds present in the permeate stream are reduced by at least 50 wt% compared to the amount present in the contaminated water; and d) recovering the enzyme from the retentate stream.
  • organofluorine compounds include polyfluoroalkyl substances.
  • organofluorine compounds include perfluoroalkyl substances.
  • a composition comprising an inorganic catalyst and a enzyme, the composition having efficacy for removing organofluorine compounds from water.
  • composition according to potential claim Pl 1 wherein the enzyme is selected from the group consisting of amylase, glutathione-S-transferase, alanine transaminase, aspartate transaminase, and combinations thereof.
  • organofluorine compounds include compounds selected from the group consisting of perfluoroalkyl substances, polyfluoroalkyl substances, and combinations thereof.
  • Pl 7. A system for removing organofluorine compounds from a stream of water, the system comprising: a water supply feed configured to provide the stream of water; an injection device, downstream of the feed water supply mechanism, configured to deliver enzyme into the stream of water; a catalytic reactor, having an inorganic catalyst disposed therein, downstream of the injection device, configured to receive the stream of water so that the stream of water mixes with the inorganic catalyst; an ultrafiltration device, configured to receive an output of the catalytic reactor, having an ultrafiltration membrane, the ultrafiltration membrane configured to separate the enzyme and any organofluorine compounds bound to the enzyme from the water stream, so as to produce (i) a permeate stream in which the organofluorine compounds arc reduced at least 50 wt% compared to the amount present in the stream of water, and (ii) a retentate stream comprising free enzyme and enzyme bound to the organofluorine compounds; and a purge control valve configured to (i) recirculate a first portion of the retentate stream into
  • the inorganic catalyst is a metal selected from the group consisting of Fe, Mg, Cr, Ti, Mn, Au, Ag, Pt, and combinations thereof.
  • P25 The system of any one of potential claims P22-P24, wherein the metal is prepared to have a high surface area.
  • P26 The system of any one of potential claims P17-P25, wherein the inorganic catalyst is Pt.

Landscapes

  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des compositions, des systèmes et des procédés pour éliminer les substances perfluoroalkylées et polyfluoroalkylées de l'eau. Les procédés de l'invention permettent d'éliminer les substances perfluoroalkylées et polyfluoroalkylées en mélangeant de l'eau contaminée avec une enzyme conjointement avec un catalyseur métallique non toxique, en filtrant le mélange, et en récupérant le catalyseur métallique à partir du flux de rétentat. L'invention concerne des procédés d'utilisation du catalyseur pour améliorer les performances de réaction tout en réduisant à un minimum la masse totale de catalyseur nécessaire au traitement. Contrairement aux procédés concurrents, le procédé décrit ici ne produit que peu ou pas de résidus.
PCT/US2025/038591 2024-07-22 2025-07-22 Destruction de substances polyfluoroalkylées à l'aide d'enzymes et de catalyseurs inorganiques Pending WO2026024681A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463673838P 2024-07-22 2024-07-22
US63/673,838 2024-07-22

Publications (2)

Publication Number Publication Date
WO2026024681A1 true WO2026024681A1 (fr) 2026-01-29
WO2026024681A9 WO2026024681A9 (fr) 2026-03-19

Family

ID=96880199

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2025/038591 Pending WO2026024681A1 (fr) 2024-07-22 2025-07-22 Destruction de substances polyfluoroalkylées à l'aide d'enzymes et de catalyseurs inorganiques

Country Status (1)

Country Link
WO (1) WO2026024681A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1238718A1 (fr) * 1999-11-11 2002-09-11 Idemitsu Kosan Company Limited Procede de degradation de matiere nocive difficilement degradable
WO2019169177A1 (fr) * 2018-03-02 2019-09-06 University Of Georgia Research Foundation, Inc. Compositions et procédés de remédiation d'acides perfluoroalkylés
US20200339450A1 (en) * 2019-04-26 2020-10-29 Geyser Remediation LLC Water Purification Apparatus and Method
EP3506997B1 (fr) * 2016-09-15 2023-06-07 Evoqua Water Technologies LLC Procédé et système de traitement d'eau ultra-pure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1238718A1 (fr) * 1999-11-11 2002-09-11 Idemitsu Kosan Company Limited Procede de degradation de matiere nocive difficilement degradable
EP3506997B1 (fr) * 2016-09-15 2023-06-07 Evoqua Water Technologies LLC Procédé et système de traitement d'eau ultra-pure
WO2019169177A1 (fr) * 2018-03-02 2019-09-06 University Of Georgia Research Foundation, Inc. Compositions et procédés de remédiation d'acides perfluoroalkylés
US20200339450A1 (en) * 2019-04-26 2020-10-29 Geyser Remediation LLC Water Purification Apparatus and Method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PILLI SRIDHAR ET AL: "Detection and removal of poly and perfluoroalkyl polluting substances for sustainable environment", JOURNAL OF ENVIRONMENTAL MANAGEMENT, ELSEVIER, AMSTERDAM, NL, vol. 297, 26 July 2021 (2021-07-26), XP086758271, ISSN: 0301-4797, [retrieved on 20210726], DOI: 10.1016/J.JENVMAN.2021.113336 *

Also Published As

Publication number Publication date
WO2026024681A9 (fr) 2026-03-19

Similar Documents

Publication Publication Date Title
Wu et al. Manganese oxide integrated catalytic ceramic membrane for degradation of organic pollutants using sulfate radicals
Lowry et al. Pd-catalyzed TCE dechlorination in groundwater: Solute effects, biological control, and oxidative catalyst regeneration
Lowry et al. Congener-specific dechlorination of dissolved PCBs by microscale and nanoscale zerovalent iron in a water/methanol solution
Wu et al. Removal of azo-dye Acid Red B (ARB) by adsorption and catalytic combustion using magnetic CuFe2O4 powder
Agarwal et al. Enhanced corrosion-based Pd/Mg bimetallic systems for dechlorination of PCBs
Andrunik et al. Comparison of pesticide adsorption efficiencies of zeolites and zeolite-carbon composites and their regeneration possibilities
Chaliha et al. Wet oxidative method for removal of 2, 4, 6-trichlorophenol in water using Fe (III), Co (II), Ni (II) supported MCM41 catalysts
Bernardi et al. Selective removal of the ammonium-nitrogen in ammonium acetate aqueous solutions by catalytic wet air oxidation over supported Pt catalysts
Choe et al. Influence of rhenium speciation on the stability and activity of Re/Pd bimetal catalysts used for perchlorate reduction
DE69311368T2 (de) Verfahren zur chemischen zersetzung von halogenierten organischen verbindungen
KR20090017677A (ko) 방향족 할로겐화물의 탈할로겐화 방법
US6464951B1 (en) Method, catalyst, and photocatalyst for the destruction of phosgene
WO2026024681A1 (fr) Destruction de substances polyfluoroalkylées à l'aide d'enzymes et de catalyseurs inorganiques
Hoareau et al. Soil remediation by nanotechnology: valuating materials, mechanisms, and environmental impacts
DE102004042793A1 (de) Verfahren zur kontinuierlichen Entfernung von oxidierbaren organischen Verbindungen aus nichtoxidierbaren Flüssigkeiten
Saeed et al. Oxidative degradation of phenol in aqueous medium catalyzed by lab prepared cobalt oxide
Santos et al. Innovative integrated catalytic system for enhanced water treatment: towards a safer future for drinking water
US4741833A (en) Method for reduction of COD in water
Hamid et al. Reduction of nitrate in groundwater by hematite supported bimetallic catalyst
JP2918542B1 (ja) 有機ハロゲン化合物の処理方法
JP2006348359A (ja) 金属の回収方法
JP4224597B2 (ja) 有害有機物を含む排水の浄化方法
JP3969633B2 (ja) 含ハロゲン有機化合物の分解処理方法
JP4920813B2 (ja) ダイオキシン類分析用活性炭含有充填剤
JP4502877B2 (ja) 硝酸還元触媒組成物およびそれを用いた硝酸溶液処理方法

Legal Events

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

Ref document number: 25760171

Country of ref document: EP

Kind code of ref document: A1