IP Library › Granted Patent US 12,186,737
Granted Patent B2
US 12,186,737 · App. 18/646,990 · Granted Jan 7, 2025

Regeneration of polymeric cyclodextrin adsorbents

Inventors: Yuhan Ling (Glenview, IL); Gokhan Barin (Wilmette, IL); Olivia Therese Teodoro (Chicago, IL); Ri Wang (Chicago, IL)
Assignee: CycloPure, Inc.
B01J20/3475B01J20/267B01J20/3085B01J20/3425B01J39/18B01J49/53
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Quick Facts
Patent No.
US 12,186,737
App. No.
18/646,990
Granted
Jan 7, 2025
Kind
B2
Abstract

Methods for removing PFAS from cationic CDP adsorbents having adsorbed PFAS are provided. The method comprises contacting a volume of the cationic CDP adsorbent with a regeneration medium and separating the cationic CDP adsorbent from the regeneration medium.

Claims (38)

1. A method of removing poly-and per-fluoroalkyl substances (PFAS) from a cationic crosslinked cyclodextrin polymer (CDP) adsorbent having adsorbed PFAS, comprising:

contacting a volume of the cationic CDP adsorbent with a regeneration medium comprising:

ethanol and water at a volumetric ratio ranging from about 1:1 to about 2:1, and

an alkali sulfate salt, an alkaline earth sulfate salt, or an ammonium sulfate salt; and

separating the cationic CDP adsorbent from the regeneration medium,

whereby at least about 50% of the total adsorbed PFAS is removed from the cationic CDP adsorbent into the regeneration medium; and

wherein the cationic CDP adsorbent is prepared by polymerizing β-cyclodextrin and a compound bearing a cationic functional group with tetrafluoroterephthalonitrile.

2. The method of claim 1 , wherein the alkali sulfate salt is Na 2 SO 4 or K 2 SO 4 .

3. The method of claim 2 , wherein the alkali sulfate salt is Na 2 SO 4 .

4. The method of claim 2 , wherein the alkali sulfate salt is K 2 SO 4 .

5. The method of claim 1 , wherein said contacting is carried out at a temperature ranging from about 20° C. to about 40° C.

6. The method of claim 2 , wherein said contacting is carried out at a temperature ranging from about 20° C. to about 40° C.

7. The method of claim 1 , wherein the adsorbed PFAS are selected from the group consisting of perfluorooctanoic acid, perfluorooctane sulfonic acid, perfluorobutane sulfonic acid, hexafluoropropylene oxide dimer acid, perfluorononanoic acid, perfluorohexane sulfonic acid, perfluorodecanoic acid, perfluorohexanoic acid, perfluorobutanoic acid, and combinations thereof.

8. The method of claim 2 , wherein the adsorbed PFAS are selected from the group consisting of perfluorooctanoic acid, perfluorooctane sulfonic acid, perfluorobutane sulfonic acid, hexafluoropropylene oxide dimer acid, perfluorononanoic acid, perfluorohexane sulfonic acid, perfluorodecanoic acid, perfluorohexanoic acid, perfluorobutanoic acid, and combinations thereof.

9. The method of claim 1 , wherein the cationic CDP adsorbent is contained in a packed-bed vessel, and the regeneration medium flows from the bottom to the top of the packed-bed vessel.

10. The method of claim 2 , wherein the cationic CDP adsorbent is contained in a packed-bed vessel, and the regeneration medium flows from the bottom to the top of the packed-bed vessel.

11. The method of claim 6 , wherein the cationic CDP adsorbent is contained in a packed-bed vessel, and the regeneration medium flows from the bottom to the top of the packed-bed vessel.

12. The method of claim 9 , wherein the regeneration medium has a flow rate at which the bed expansion rate ranges from about 30% to about 50%.

13. The method of claim 10 , wherein the regeneration medium has a flow rate at which the bed expansion rate ranges from about 30% to about 50%.

14. The method of claim 11 , wherein the regeneration medium has a flow rate at which the bed expansion rate ranges from about 30% to about 50%.

15. The method of claim 1 , wherein the PFAS removed from the cationic CDP adsorbent is further concentrated using a method selected from the group consisting of membrane filtration, distillation, evaporation, and combinations thereof.

16. The method of claim 1 , wherein the sulfate salt is present in the regeneration medium at a concentration from about 0.2 g/L to about 0.5 g/L.

17. The method of claim 3 , wherein the Na 2 SO 4 is present in the regeneration medium at a concentration from about 0.2 g/L to about 0.5 g/L.

18. The method of claim 4 , wherein the K 2 SO 4 is present in the regeneration medium at a concentration from about 0.2 g/L to about 0.5 g/L.

19. A method of removing PFAS from a cationic CDP adsorbent having adsorbed PFAS, comprising:

contacting a volume of the cationic CDP adsorbent with a regeneration medium comprising:

ethanol and water at a volumetric ratio ranging from about 1:1 to about 2:1, and

Na 2 SO 4 which is present at a concentration of about 0.5 g/L; and

separating the cationic CDP adsorbent from the regeneration medium,

whereby at least about 50% of the total adsorbed PFAS is removed from the cationic CDP adsorbent into the regeneration medium; and

wherein the cationic CDP adsorbent is prepared by polymerizing β-cyclodextrin and a compound bearing a cationic functional group with tetrafluoroterephthalonitrile.

20. A method of removing PFAS from a cationic CDP adsorbent having adsorbed PFAS, comprising:

contacting a volume of the cationic CDP adsorbent with a regeneration medium comprising:

ethanol and water at a volumetric ratio ranging from about 1:1 to about 2:1, and

K 2 SO 4 which is present at a concentration of about 0.5 g/L; and

separating the cationic CDP adsorbent from the regeneration medium,

whereby at least about 50% of the total adsorbed PFAS is removed from the cationic CDP adsorbent into the regeneration medium; and

wherein the cationic CDP adsorbent is prepared by polymerizing β-cyclodextrin and a compound bearing a cationic functional group with tetrafluoroterephthalonitrile.

Assignments (2)
SECURITY INTEREST Recorded Dec 23, 2024
From: CYCLOPURE, INC.
To: AVENUE GLOBAL DISLOCATION OPPORTUNITIES FUND, L.P. AND AVENUE GLOBAL OPPORTUNITIES MASTER FUND, L.P.; AVENUE GLOBAL DISLOCATION OPPORTUNITIES FUND, L.P. AND AVENUE GLOBAL OPPORTUNITIES MASTER FUND, L.P.
Reel/Frame 069668/0780 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 26, 2024
From: LING, YUHAN; BARIN, GOKHAN; TEODORO, OLIVIA THERESE; WANG, RI
To: CYCLOPURE, INC.
Reel/Frame 067241/0684 →
Continuity (3)
Continuation 18410056 · Jan 11, 2024
Provisional Application 63479611 · Jan 12, 2023
Related Publication 20240293801A1 · Sep 5, 2024
References Cited (117)
US 3426011A · Parmerter et al. · 1969 [cited by applicant]
US 3453257A · Parmerter et al. · 1969 [cited by applicant]
US 3453258A · Parmerter et al. · 1969 [cited by applicant]
US 3453259A · Parmerter et al. · 1969 [cited by applicant]
US 3453260A · Parmerter et al. · 1969 [cited by applicant]
US 3459731A · Gramera et al. · 1969 [cited by applicant]
US 3553191A · Parmerter et al. · 1971 [cited by applicant]
US 3565887A · Parmerter et al. · 1971 [cited by applicant]
US 4535152A · Szejtli et al. · 1985 [cited by applicant]
US 4565727A · Giglia et al. · 1986 [cited by applicant]
US 4616008A · Hirai et al. · 1986 [cited by applicant]
US 4638058A · Brandt et al. · 1987 [cited by applicant]
US 4678598A · Ogino et al. · 1987 [cited by applicant]
US 4746734A · Tsuchiyama et al. · 1988 [cited by applicant]
US 5183809A · Weisz et al. · 1993 [cited by applicant]
US 5262404A · Weisz et al. · 1993 [cited by applicant]
US 5488021A · DeLiso et al. · 1996 [cited by applicant]
US 5496649A · Mallory et al. · 1996 [cited by applicant]
US 6444723B1 · Kline · 2002 [cited by applicant]
US 6881712B2 · Angell et al. · 2005 [cited by applicant]
US 9828458B2 · Suri et al. · 2017 [cited by applicant]
US 10287185B2 · Nickelsen et al. · 2019 [cited by applicant]
US 11001645B2 · Barin et al. · 2021 [cited by applicant]
US 11155646B2 · Barin et al. · 2021 [cited by applicant]
US 11512146B2 · Barin et al. · 2022 [cited by applicant]
US 20010008222A1 · Ma et al. · 2001 [cited by applicant]
US 20050154198A1 · Trotta et al. · 2005 [cited by applicant]
US 20050262646A1 · Berlinger · 2005 [cited by applicant]
US 20060067965A1 · Chandra et al. · 2006 [cited by applicant]
US 20100311905A1 · Mentink et al. · 2010 [cited by applicant]
US 20140178457A1 · Travaglini et al. · 2014 [cited by applicant]
US 20150004389A1 · Corinti et al. · 2015 [cited by applicant]
US 20150273389A1 · Liu et al. · 2015 [cited by applicant]
US 20150361595A1 · Keane et al. · 2015 [cited by applicant]
US 20160304630A1 · Dichtel et al. · 2016 [cited by applicant]
US 20160370357A1 · Lucas et al. · 2016 [cited by applicant]
US 20170173560A1 · Dichtel et al. · 2017 [cited by applicant]
US 20170222458A1 · Chang et al. · 2017 [cited by applicant]
US 20180186939A1 · Blanchemain et al. · 2018 [cited by applicant]
US 20190015814A1 · Trabolsi et al. · 2019 [cited by applicant]
US 20190375858A1 · Xie et al. · 2019 [cited by applicant]
US 20200071530A1 · Birkeland · 2020 [cited by applicant]
US 20200262936A1 · Barin et al. · 2020 [cited by applicant]
US 20200306726A1 · James et al. · 2020 [cited by applicant]
US 20200398252A1 · Ma et al. · 2020 [cited by applicant]
US 20210163631A1 · Barin et al. · 2021 [cited by applicant]
US 20220017645A1 · Barin et al. · 2022 [cited by applicant]
US 20230279158A1 · Barin et al. · 2023 [cited by applicant]
US 20240238761A1 · Ling et al. · 2024 [cited by applicant]
CN 1352199A · 2002 [cited by applicant]
CN 1658888A · 2005 [cited by applicant]
CN 101733009A · 2010 [cited by applicant]
CN 102659206A · 2012 [cited by applicant]
CN 107376875A · 2017 [cited by applicant]
CN 107709251A · 2018 [cited by applicant]
CN 107709441A · 2018 [cited by applicant]
CN 108554387A · 2018 [cited by applicant]
CN 108579689A · 2018 [cited by applicant]
CN 109046280A · 2018 [cited by applicant]
CN 109053932A · 2018 [cited by applicant]
JP 2005125193A · 2005 [cited by applicant]
JP 2006083379A · 2006 [cited by applicant]
JP 2010119389A · 2010 [cited by applicant]
JP 2013233473A · 2013 [cited by applicant]
JP 2019218535A · 2019 [cited by applicant]
KR 20100122880A · 2010 [cited by applicant]
WO WO2012090018A1 · 2012 [cited by applicant]
WO WO2016172118A1 · 2016 [cited by applicant]
WO WO2018200857A1 · 2018 [cited by applicant]
WO WO2020073674A1 · 2020 [cited by applicant]
WO WO2020167375A1 · 2020 [cited by applicant]
WO WO2022018472A1 · 2022 [cited by applicant]
Deng, Shubo, et al. “Enhanced adsorption of perfluorooctane sulfonate and perfluorooctanoate by bamboo-derived granular activated carbon.” Journal of hazardous materials 282 (2015): 150-157. [cited by examiner]
Ling, Yuhan, et al. “Novel Cyclodextrin Polymer Adsorbents for PFAS Removal.” Forever Chemicals. CRC Press, 2021. 291-313. [cited by examiner]
Helbling, Damian, and William R. Dichtel. “Rational Design and Implementation of Novel Polymer Adsorbents for Selective Uptake of PFAS from Groundwater.” (2022): 120. [cited by examiner]
Vakili, Mohammadtaghi, et al. “Regeneration of chitosan-based adsorbents used in heavy metal adsorption: A review.” Separation and Purification Technology 224 (2019): 373-387. [cited by examiner]
Boyer, Treavor H., et al. “Life cycle environmental impacts of regeneration options for anion exchange resin remediation of PFAS impacted water.” Water research 207 (2021): 117798. [cited by examiner]
Lin, Wei. Dynamic modeling of the biological activated carbon (BAC) process and its experimental corroboration. State University of New York at Buffalo, 1992. [cited by examiner]
Klemes, Max. Understanding and Designing Cyclodextrin Adsorbents for Water Purification. Diss. Northwestern University, 2020. [cited by examiner]
Trang, Brittany. Methods and Mechanisms for Per-and Polyfluoroalkyl Substance (PFAS) Removal and Degradation. Diss. Northwestern University, 2022. [cited by examiner]
Alsbaiee et al., Rapid removal of organic micropollutants from water by a porous beta-cyclodextrin polymer; Nature vol. 529, pp. 190-194. Dec. 21, 2015. [cited by applicant]
Alzate-Sanchez et al. “Cotton Fabric Functionalized with a—Cyclodextrin Polymer Captures Organic Pollutants from Contaminated Air and Water,” Chem. Mater. 2016, 28, 8340-8346. [cited by applicant]
Anne, J.M., et al., “β-Cyclodextrin Conjugated Bifunctional Isocyanate Linker Polymer for Enhanced Removal of 2,4-Dinitrophenol from Environmental Waters,” Royal Society Open Science, 2018, vol. 5, 180942, 22 pages. [cited by applicant]
Barry et al., “Perfluorooctanoic Acid (PFOA) Exposures and Incident Cancers Among Adults Living Near a Chemical Plant,” Environ. Health Perspect. 2013, 121(11-12):1313-1318. [cited by applicant]
Barzen-Hanson et al., “Discovery of 40 Classes of Per-And Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater,” Environ. Sci. Technol. 2017, 51, 2047-2057. [cited by applicant]
Berto S., et al., “Synthesis of new iconic β-cyclodextrin polymers and characterization of their heavy metals retentions,” Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2007, vol. 57, pp. 631-636. [cited by applicant]
Carpenter et al., “Widespread Micropollutant Monitoring in the Hudson River Estuary Reveals Spatiotemporal Micropollutant Clusters and Their Sources,” Environ. Sci. Technol. 2018, 52, 6187-6196. [cited by applicant]
Co-pending U.S. Appl. No. 18/410,056, inventors Ling; Yuhan et al., filed on Jan. 11, 2024. [cited by applicant]
D'Agostino et al., “Certain Perfluoroalkyl and Polyfluoroalkyl Substances Associated With Aqueous Film Forming Foam Are Widespread in Canadian Surface Waters,” Environ. Sci. Technol. 2017, 51, 13603-13613. [cited by applicant]
Deng et al., “Removal of perfluorooctane sulfonate from wastewater by anion exchange resins: effects of resin properties and solution chemistry,” Water Research 44:5188-5195 (Oct. 2010). [cited by applicant]
Diamanti-Kandarakis et al., “Endocrine-Disrupting Chemicals: an Endocrine Society Scientific Statement,” Endocr. Rev. 2009, 30, 293-342. [cited by applicant]
Diedaini-Pilard and Perly, “Optimal Performances with Minimal Chemical Modification of Cyclodextrins,” The 7th International Cyclodextrin Symposium Abstracts, p. 49 (Apr. 1994). [cited by applicant]
Du et al., “Adsorption behavior and mechanism of perfluorinated compounds on various adsorbents—a review,” Journal of Hazardous Materials 274:443-454 (Jun. 2014). [cited by applicant]
Fan D., et al., “Research on β-Cyclodextrin Cross-Linked Polymers Removing Chlorobenzene and Nitrobenzene in Micro-Polluted Water”, Environmental Science & Technology, Dec. 15, 2010, pp. 258-260. [cited by applicant]
Folch-Cano, C et al., “Inclusion and Functionalization of Polymers with Cyclodextrins: Current Applications and Future Prospects,” Molecules 19:14066-14079 (2014). [cited by applicant]
Gallo et al., “Serum Perfluorooctanoate (PFOA) and Perfluorooctane Sulfonate (PFOS) Concentrations and Liver Function Biomarkers in a Population With Elevated PFOA Exposure,” Environ. Health Perspect. 2012, 120, 655-660. [cited by applicant]
Hishiya, T., et al., “Molecularly Imprinted Cyclodextrin Polymers as Stationary Phases of HighPerformance Liquid Chromatography,” Polymer Journal, 2003, vol. 35, No. 5, pp. 440-445. [cited by applicant]
Hu et al., “Detection of Poly-and Perfluoroalkyl Substances (PFASs) in U.S. Drinking Water Linked to Industrial Sites, Military Fire Training Areas, and Wastewater Treatment Plants,” Environ. Sci. Technol. Lett. 2016, 3… [cited by applicant]
International Search Report and Written Opinion for PCT Application No. PCT/US2024/011236 dated Apr. 17, 2024, 10 pages. [cited by applicant]
International Search Report and Written Opinion issued by the International Searching Authority for Application No. PCT/US2020/018149, dated Apr. 20, 2020, 10 pages. [cited by applicant]
Ji et al., “Removal of GenX and Perfluorinated Alkyl Substances from Water by Amine-Functionalized Covalent Organic Frameworks,” Am. Chem. Soc. 2018, 140, 12677-12681. [cited by applicant]
Kawano, S., et al., “Adsorption Capability of Urethane-Crosslinked Heptakis (2,6-di-O-methyl)-β-Cyclodextrin Polymers Toward Polychlorobiphenyls in Nonpolar Organic Media,” Polymer Journal, 2015, vol. 47, pp. 443-448. [cited by applicant]
Kleme et al., “Phenolation of cyclodextrin polymers controls their lead and organic micropollutant adsorption,” Chem. Sci. 2018, 9, 8883-8889. [cited by applicant]
Li et al., “Phenolation of cyclodextrin polymers controls their lead and organic micropollutant adsorption,” J. Chromatogr. A 2018, 1541, 52-56. [cited by applicant]
Ling et al., “Benchmarking Micropollutant Removal by Activated Carbon and Porous—Cyclodextrin Polymers Under Environmentally Relevant Scenarios,” Environ. Sci. Technol. 2017, 51, 7590-7598. [cited by applicant]
Mason et al., “Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification,” Macromolecules 2014, 47:1021-1029. [cited by applicant]
Melzer et al., “Association Between Serum Perfluorooctanoic Acid (PFOA) and Thyroid Disease in the U.S. National Health and Nutrition Examination Survey,” Environ. Health Perspect. 2010, 118, 686-692. [cited by applicant]
Raoov et al., “Synthesis and Characterization of ß-Cyclodextrin Functionalized Ionic Liquid Polymer as a Macroporous Material for the Removal of Phenols and As(V),” Int. J. Mol. Sci. 15(1):100-119 (2014). [cited by applicant]
Research on Rural Water Environment Ecological Management Model, First Edition, Liangping Deng et al., pp. 77-78, Yellow River Water Conservation Press. [cited by applicant]
Richardson et al., “Water Analysis: Emerging Contaminants and Current Issues,” Anal. Chem. 2018, 90, 398-428. [cited by applicant]
Sun et al., “Legacy and Emerging Perfluoroalkyl Substances are Important Drinking Water Contaminants in the Cape Fear River Watershed of North Carolina,” Environ. Sci. Technol. Lett. 2016, 3, 415-419. [cited by applicant]
Tetreault et al., “Intersex and Reproductive Impairment of Wild Fish Exposed to Multiple Municipal Wastewater Discharges,” Toxicol. 2011, 104, 278-290. [cited by applicant]
Xiao et al., “Cross-linker Chemistry Determines the Uptake Potential of Perfluorinated Alkyl Substances by -Cyclodextrin Polymers,” Macromolecules 52(10):3747-3752 (2019). [cited by applicant]
Xiao et al., “Cyclodextrin Polymer Network Sequesters Perfluorooctanoic Acid at Environmentally Relevant Concentrations,” Am. Chem. Soc. 139:7689-7692 (2017). [cited by applicant]
Yang, S.Y., et al., “Synthesis and Characterization of Cationic and Anionic Cyclodextrin Oligomaers and Their Use in Layer-by-Layer Film Formation,” Bulletin of the Korean Chemical Society 34:2016-2022 (2013). [cited by applicant]
Gobindlal et al., “Solvent-Free, Ambient Temperature and Pressure Destruction of Perfluorosulfonic Acids under Mechanochemical Conditions: Degradation Intermediates and Fluorine Fate,” Environ Sci Technol. 57(1):277-285… [cited by applicant]
Kah et al., “Sequestration and potential release of PFAS from spent engineered sorbents,” Sci Total Environ. 765:142770, pp. 1-10. (Apr. 15, 2021). Epub Oct. 7, 2020. [cited by applicant]