Adsorbent having high volume iodine value and molasses value for removing PFAS from fluids, and method for producing and using the same.

Abstract

The present disclosure provides adsorbents and sorbents that improve the adsorption of perfluoroalkyl and polyfluoroalkyl substances (PFAS). The adsorbents and sorbents have a microstructure that efficiently adsorbs PFAS, as evidenced by a combination of a high volumetric iodine number and a high volumetric molasses number. Methods of manufacture and use are also provided.

Description

[Technical Field]

[0001] Reference to related applications Claiming the interests of U.S. Provisional Patent Application No. 63 / 051,637, filed on 14 July 2020, which is incorporated herein by reference in its entirety.

[0002] This disclosure describes adsorbents having improved performance in removing perfluoroalkyl and polyfluoroalkyl substances, including but not limited to PFOA, PFOS, and similar compounds, from liquids and gases. [Background technology]

[0003] Perfluoroalkyl substances (PFAS) are a group of compounds that include perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and compounds produced by the gENX process, such as 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid and heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether. Such highly fluorinated compounds have been widely used industrially for many years due to their chemical durability, excellent surfactant properties, and important role as precursors for fluoropolymers, including polytetrafluoroethylene.

[0004] Unfortunately, these similar properties make perfluoroalkyl and polyfluoroalkyl substances resistant to degradation in the environment, leading to bioaccumulation over time if ingested. Several recent studies have linked perfluoroalkyl and polyfluoroalkyl substances to a variety of harmful health effects, particularly elevated cholesterol levels, as well as kidney cancer, testicular cancer, thyroid disorders, and pregnancy-induced hypertension.

[0005] To date, various techniques have been employed to remove perfluoroalkyl and polyfluoroalkyl substances from the environment and drinking water, but none have been completely satisfactory. For example, some prior art has attempted to remove perfluoroalkyl and polyfluoroalkyl substances by contacting fluids containing them with various adsorbents. However, prior art has failed to explain which chemical and microstructural properties of the adsorbents lead to or do not lead to the effective capture of perfluoroalkyl and polyfluoroalkyl substances. Therefore, there remains not only a need for more effective adsorbents themselves to better remove perfluoroalkyl and polyfluoroalkyl substances from the environment and drinking water, but also a need for materials designed to have the desired chemical and microstructural properties. The following are prior art documents related to the invention of this application (including documents cited in the international phase after the international filing date and documents cited when the application entered the national phase in other countries): (Prior art document) (Patent Document) (Patent Document 1) U.S. Patent Application Publication No. 2012 / 0172216 (Patent Document 2) U.S. Patent Application Publication No. 2017 / 0297926 Specification (Patent Document 3) U.S. Patent No. 5,248,395 (Patent Document 4) U.S. Patent No. 2,038,071 (Patent Document 5) U.S. Patent Application Publication No. 2002 / 0170436 Specification (Patent Document 6) U.S. Patent Application Publication No. 2003 / 0188663 (Patent Document 7) U.S. Patent Application Publication No. 2004 / 0118287 (Patent Document 8) U.S. Patent Application Publication No. 2004 / 0118387 (Patent Document 9) U.S. Patent Application Publication No. 2005 / 0081717 (Patent Document 10) U.S. Patent Application Publication No. 2005 / 0167367 (Patent Document 11) U.S. Patent Application Publication No. 2006 / 0042467 (Patent Document 12) U.S. Patent Application Publication No. 2006 / 0054142 (Patent Document 13) U.S. Patent Application Publication No. 2007 / 0169758 (Patent Document 14) U.S. Patent Application Publication No. 2007 / 0272080 Specification (Patent Document 15) U.S. Patent Application Publication No. 2008 / 0073290 Specification (Patent Document 16) U.S. Patent Application Publication No. 2008 / 0121142 (Patent Document 17) U.S. Patent Application Publication No. 2008 / 0283446 (Patent Document 18) U.S. Patent Application Publication No. 2008 / 0308075 (Patent Document 19) U.S. Patent Application Publication No. 2009 / 0172998 Specification (Patent Document 20) U.S. Patent Application Publication No. 2009 / 0223370 Specification (Patent Document 21) U.S. Patent Application Publication No. 2010 / 0178624 (Patent Document 22) U.S. Patent Application Publication No. 2011 / 0030592 Specification (Patent Document 23) U.S. Patent Application Publication No. 2011 / 0076210 (Patent Document 24) U.S. Patent Application Publication No. 2012 / 0048110 (Patent Document 25) U.S. Patent Application Publication No. 2012 / 0100054 (Patent Document 26) U.S. Patent Application Publication No. 2012 / 0172216 (Patent Document 27) U.S. Patent Application Publication No. 2012 / 0220451 (Patent Document 28) U.S. Patent Application Publication No. 2013 / 0078169 (Patent Document 29) U.S. Patent Application Publication No. 2013 / 0109562 Specification (Patent Document 30) U.S. Patent Application Publication No. 2013 / 0168321 (Patent Document 31) U.S. Patent Application Publication No. 2013 / 0269532 (Patent Document 32) U.S. Patent Application Publication No. 2013 / 0316433 (Patent Document 33) U.S. Patent Application Publication No. 2014 / 0117054 (Patent Document 34) U.S. Patent Application Publication No. 2014 / 0165542 (Patent Document 35) U.S. Patent Application Publication No. 2014 / 0112856 Specification (Patent Document 36) U.S. Patent Application Publication No. 2014 / 0336568 (Patent Document 37) U.S. Patent Application Publication No. 2015 / 0050202 Specification (Patent Document 38) U.S. Patent Application Publication No. 2016 / 0023920 (Patent Document 39) U.S. Patent Application Publication No. 2016 / 0166972 (Patent Document 40) U.S. Patent Application Publication No. 2016 / 0167982 (Patent Document 41) U.S. Patent Application Publication No. 2016 / 0236169 (Patent Document 42) U.S. Patent Application Publication No. 2016 / 0271555 Specification (Patent Document 43) U.S. Patent Application Publication No. 2016 / 0346723 (Patent Document 44) U.S. Patent Application Publication No. 2017 / 0297926 Specification (Patent Document 45) U.S. Patent Application Publication No. 2018 / 0030871 (Patent Document 46) U.S. Patent Application Publication No. 2018 / 0214816 (Patent Document 47) U.S. Patent Application Publication No. 2019 / 0201870 Specification (Patent Document 48) U.S. Patent Application Publication No. 2019 / 0247831 (Patent Document 49) U.S. Patent Application Publication No. 2019 / 0270081 (Patent Document 50) U.S. Patent Application Publication No. 2020 / 0038798 Specification (Patent Document 51) U.S. Patent Application Publication No. 2020 / 0039809 (Patent Document 52) ​​U.S. Patent Application Publication No. 2020 / 0040851 (Patent Document 53) U.S. Patent Application Publication No. 2020 / 0179902 Specification (Patent Document 54) U.S. Patent Application Publication No. 2020 / 0316560 Specification (Patent Document 55) U.S. Patent No. 3,713,281 (Patent Document 56) U.S. Patent No. 3,757,488 (Patent Document 57) U.S. Patent No. 4,331,639 (Patent Document 58) U.S. Patent No. 4,624,937 (Patent Document 59) U.S. Patent No. 4,921,826 (Patent Document 60) U.S. Patent No. 5,016,628 (Patent Document 61) U.S. Patent No. 5,248,395 (Patent Document 62) U.S. Patent No. 5,322,778 (Patent Document 63) U.S. Patent No. 5,338,458 (Patent Document 64) U.S. Patent No. 5,348,755 (Patent Document 65) U.S. Patent No. 5,352,274 (Patent Document 66) U.S. Patent No. 5,356,849 (Patent Document 67) U.S. Patent No. 5,500,038 (Patent Document 68) U.S. Patent No. 5,504,050 (Patent Document 69) U.S. Patent No. 5,598,721 (Patent Document 70) U.S. Patent No. 5,754,002 (Patent Document 71) U.S. Patent No. 5,821,682 (Patent Document 72) U.S. Patent No. 5,861,050 (Patent Document 73) U.S. Patent No. 6,176,897 (Patent Document 74) U.S. Patent No. 6,186,939 (Patent Document 75) U.S. Patent No. 6,342,129 (Patent Document 76) U.S. Patent No. 6,406,523 (Patent Document 77) U.S. Patent No. 6,599,856 (Patent Document 78) U.S. Patent No. 6,699,393 (Patent Document 79) U.S. Patent No. 6,706,194 (Patent Document 80) U.S. Patent No. 6,848,374 (Patent Document 81) U.S. Patent No. 7,222,612 (Patent Document 82) U.S. Patent No. 7,278,406 (Patent Document 83) U.S. Patent No. 7,361,280 (Patent Document 84) U.S. Patent No. 7,547,350 (Patent Document 85) U.S. Patent No. 7,666,507 (Patent Document 86) U.S. Patent No. 7,704,305 (Patent Document 87) U.S. Patent No. 7,077,891 (Patent Document 88) U.S. Patent No. 7,780,765 (Patent Document 89) U.S. Patent No. 7,858,061 (Patent Document 90) U.S. Patent No. 7,862,725 (Patent Document 91) U.S. Patent No. 7,879,136 (Patent Document 92) U.S. Patent No. 7,923,410 (Patent Document 93) U.S. Patent No. 8,034,163 (Patent Document 94) U.S. Patent No. 8,042,524 (Patent Document 95) U.S. Patent No. 8,057,576 (Patent Document 96) U.S. Patent No. 8,069,797 (Patent Document 97) U.S. Patent No. 8,080,088 (Patent Document 98) U.S. Patent No. 8,168,147 (Patent Document 99) U.S. Patent No. 8,263,524 (Patent Document 100) U.S. Patent No. 8,864,877 (Patent Document 101) U.S. Patent No. 9,120,079 (Patent Document 102) U.S. Patent No. 9,174,205 (Patent Document 103) U.S. Patent No. 9,199,862 (Patent Document 104) U.S. Patent No. 9,732,649 (Patent Document 105) U.S. Patent No. 10,155,673 (Patent Document 106) U.S. Patent No. 11,872,539 (Patent Document 107) U.S. Patent No. 11,911,743 (Patent Document 108) Canadian Patent Application Publication No. 2485103 (Patent Document 109) Specification of Chinese Patent Application Publication No. 108940191 (Patent Document 110) German Patent No. 3620425, Specification 4 (Patent Document 111) European Patent Application Publication No. 0433677 Specification (Patent Document 112) European Patent Application Publication No. 1413348 (Patent Document 113) European Patent Application Publication No. 1521723 (Patent Document 114) Specification of French Patent Application Publication No. 3077069 (Patent Document 115) Specification of British Patent Application No. 1336241 (Patent Document 116) JP-A-01-58331 (Patent Document 117) Japanese Unexamined Patent Publication No. 2008-023365 (Patent Document 118) Korean Published Patent No. 2012-0074080 (Patent Document 119) International Publication No. 1981 / 000399 (Patent Document 120) International Publication No. 2010 / 042321 (Patent Document 121) International Publication No. 2009 / 031562 (Patent Document 122) International Publication No. 2011 / 038415 (Patent Document 123) International Publication No. 2011 / 127323 (Patent Document 124) International Publication No. 2013 / 063490 (Patent Document 125) International Publication No. 2013 / 096281 (Patent Document 126) International Publication No. 2013 / 149241 (Patent Document 127) International Publication No. 2014 / 082076 (Patent Document 128) International Publication No. 2014 / 088630 (Patent Document 129) International Publication No. 2014 / 335658 (Patent Document 130) International Publication No. 2014 / 205200 (Patent Document 131) International Publication No. 2016 / 185033 (Patent Document 132) International Publication No. 2017 / 180346 (Patent Document 133) International Publication No. 2018 / 116842 (Patent Document 134) International Publication No. 2018 / 175936 (Patent Document 135) International Publication No. 2018 / 144588 (Patent Document 136) International Publication No. 2020 / 028839 (Patent Document 137) International Publication No. 2020 / 028703 (Patent Document 138) International Publication No. 2020 / 028845 (Non-Patent Document) (Non-Patent Document 1) McNAMARA et al. "Comparison of Activated Carbons for Removal of Perfluorinated Compounds From Drinking Water" (ARTICLE in JOURNAL AWWA) (Published in JANUARY 2018) Retrieved from the internet on September 22, 2021. url <https: / / cswab.org / wp-content / uploads / 2018 / 12 / Activated-Carbons-Comparison-for-Removal-of-PFAS-in-Drinking-Water-McNamara-2018.pdf> Entire document, abstract; pg 3, col 2 para 4 to pg 4, col 1 para 1; pg 4, Table 3; pg 4, col 2, para 2. pg 5, col 2, para 5; pg 7, col 2, para 4; pg 9, col 1, para 1 (Non-patent document 2) "The Chemistry of Nitrogen and Phosphorus." Purdue Chemistry, Purdue University, 2006, chemed.chem.purdue.edu / genchem.topicreview / bp / ch10 / group5.php#negative. (Non-patent document 3) APPLEMAN et al. "Treatment Of Poly- and Perfluoroalkyl Substances In US Full-scale Water Treatment Systems" 2014, Water Research 51: 246-255 (Non-patent document 4) BARRIOS-BERMUDEZ et al. "Fe-Cu Doped Multiwalled Carbon Nanotubes for Fenton-like Degradation of Paracetamol under Mild Conditions" April 14, 2020, Nanomaterials 10(749):1-18 (Non-Patent Document 5) JOHNSON et al., "Advanced Filtration Membranes for the Removal of Perfluoroalkyl Species from Water", American Chemical Society, ACS Omega, May 2, 2019, Vol. 4(5), pp. 8001-8006 (Non-patent document 6) Pietrzak et al. "Preparation of Nitrogen-Enriched Activated Carbons from Brown Coal" 2006, Energy & Fuels 20:1275-1280 (Non-patent document 7) RAPOSO et al., Mercury Speciation in Fluorescent Lamps by Thermal Release Analysis (2003), Waste Management 23(10):879-886 (Non-Patent Document 8) Sharifi et al., "Formation of Active Sites for Oxygen Reduction Reations by Transmation of Nitrogen Functionalities in Nitrogen-Doped Carbon Nanotubes." ACS Nano,Vol.6,No.10,2012,pp.8904-8912,doi:10.1021 / nn302906r (Non-Patent Document 9) SONTHEIMER et al. "Evaluation Methods Utilizing Aqueous Solutions, In Activated Carbon For Water Treatment" 1988, DVGW-Forschungsstelle Second Edition 100-105 (Non-patent document 10) WANG et al., "Influence of cations on the partition behavior of perfluoroheptanoate (PFHpA) and perfluorohexanesulfonate (PFHxS) on wastewater sludge", Chemosphere, Vol.131, July 2015, pp.178-183 (Non-Patent Document 11) WESTREICH et al., "The removal of short-chain and long-chain perfluoroalkyl acids and sulfonates via granular activated carbons: A comparative column study", Remediation Journal, December 4,2018; Vol.29(1) pp.19-26 (Non-patent document 12) XU, et al., "Journal of Colloid and Interface Science 2018, 523, 144-150 (Year: 2018) [Overview of the project]

[0006] This disclosure provides an adsorbent for removing one or more perfluoroalkyl and polyfluoroalkyl substances from a fluid. In one embodiment, this disclosure provides an adsorbent for removing one or more perfluoroalkyl and polyfluoroalkyl substances from a fluid, the adsorbent having a concentration of approximately 450 mg / cm³. 3 ~about 550mg / cm 3 The volumetric iodine value and approximately 100 cm³ -3 ~about 400cm -3 This shows the volumetric molasses value.

[0007] In one embodiment, the adsorbent includes one or more of carbonaceous char, activated carbon, reactivated carbon, and carbon black.

[0008] In another embodiment, the adsorbent comprises one or both activated carbon and reactivated carbon, which in any embodiment may be formed from precursor carbonaceous materials selected from bituminous coal, subbituminous coal, lignite, brown coal, anthracite, wood, wood chips, sawdust, peat, nut shells, pits, coconut shells, babassu nuts, macadamia nuts, dendezza nuts, peach pits, cherry pits, olive pits, walnut shells, wood, lignin, polymers, nitrogen-containing polymers, resins, petroleum pitch, bagasse, rice husks, corn husks, wheat husks and rice husks, graphene, carbon nanotubes, and polymer fibers.

[0009] In another embodiment, the activated carbon or reactivated carbon is formed from one or both bituminous and subbituminous carbon.

[0010] In another embodiment, the activated carbon or reactivated carbon is re-aggregated.

[0011] In another embodiment, the adsorbent is approximately 450 mg / cm³. 3 ~about 600mg / cm 3 The volumetric iodine value, and approximately 100 cm³ -3 ~about 400cm 3has a volumetric iodine value.

[0012] In another embodiment, a bed containing an adsorbent removes PFOA from at least about 20,000 bed volumes of water containing PFOA at a concentration of about 61 ng / L or less, thereby being able to generate a filtered water stream before PFOA at a concentration of about 15 ng / L is detected in the filtered water stream.

[0013] In another aspect, the present disclosure provides a method for removing one or more perfluoroalkyl and polyfluoroalkyl substances from a fluid, the method comprising providing an adsorbent having a volumetric iodine value of at least about 450 mg / cm 3 and a volumetric molasses value of at least about 100 cm -3 and contacting the fluid with the adsorbent.

[0014] In one embodiment, the adsorbent comprises one or more of carbonaceous char, activated carbon, reactivated carbon, and carbon black.

[0015] In another embodiment, the adsorbent comprises one or both of activated carbon or reactivated carbon.

[0016] In another embodiment, the activated carbon or reactivated carbon is formed from a precursor carbonaceous material selected from bituminous coal, sub-bituminous coal, lignite, peat, anthracite, wood, wood chips, sawdust, peat, nut shells, pits, coconut shells, babassu nuts, macadamia nuts, dendena nuts, peach pits, cherry pits, olive pits, walnut shells, wood, lignin, polymers, nitrogen-containing polymers, resins, petroleum pitch, bagasse, rice husks, corn husks, wheat husks and rice husks, graphene, carbon nanotubes, polymer fibers.

[0017] In another embodiment, the activated carbon or reactivated carbon is formed from one or more of bituminous coal and sub-bituminous coal.

[0018] In another embodiment, the activated carbon or reactivated carbon is re-aggregated.

[0019] In another embodiment, the adsorbent is approximately 450 mg / cm³. 3 ~about 600mg / cm 3 The volumetric iodine value, and approximately 100 cm³ -3 ~about 400cm -3 It has a volumetric molasses value.

[0020] In another embodiment, the adsorbent is approximately 500 mg / cm³. 3 ~about 550mg / cm 3 The volumetric iodine value, and approximately 110 cm³ 3 ~about 350cm 3 It has a volumetric molasses value.

[0021] In another embodiment, a bed containing an adsorbent can remove PFOA from at least about 20,000 bed volume of water containing PFOA at a concentration of about 61 ng / L or less, thereby generating a filtered water stream before PFOA at a concentration of about 15 ng / L is detected in the filtered water stream.

[0022] In another aspect, this disclosure contains at least about 450 mg / cm³ 3 The volumetric iodine value and at least about 100 cm³ -3 The present invention provides an adsorbent composition comprising one or more adsorbents having a volume molasses value and optionally a second adsorbent.

[0023] In one embodiment, the adsorbent composition comprises one or more inert materials, fillers, binders, or other compositions that do not possess any significant adsorbent capacity.

[0024] In another embodiment, the adsorbent is approximately 450 mg / cm³. 3 ~about 600mg / cm 3 The volumetric iodine value, and approximately 100 cm³ -3 ~about 400cm -3 It has a volumetric molasses value.

[0025] In another embodiment, the adsorbent is approximately 500 mg / cm³. 3 ~about 550mg / cm 3 The volumetric iodine value, and approximately 110 cm³ 3~about 350cm 3 It has a volumetric molasses value.

[0026] In another embodiment, a bed containing an adsorbent composition can remove PFOA from at least about 20,000 bed volumes of water containing PFOA at a concentration of about 61 ng / L or less, thereby generating a filtered water stream before PFOA at a concentration of about 15 ng / L is detected in the filtered water stream. [Brief explanation of the drawing]

[0027] The aspects, features, benefits, and advantages of the embodiments described herein will become apparent with respect to the following description, the appended claims, and the appended drawings.

[0028] [Figure 1] Figure 1 provides an example of a decolorization curve for a sample of an adsorbent as disclosed herein.

[0029] [Figure 2] Figure 2 shows the UV-Vis transmittance spectra collected from samples of the filtrate of the molasses solution after treatment with activated carbon.

[0030] [Figure 3] Figure 3 provides a plot of perfluorooctanoic acid (PFOA) concentrations measured in water at the outlet ports of adsorbent beds containing adsorbents of various molasses values, normalized to the number of bed volumes of untreated water and water that passed through the bed.

[0031] [Figure 4A] Figure 4A provides a scatter plot of the volume molasses value and volume iodine value of various adsorbents, as described herein, when the concentration of PFOA in the water at the floor outlet port reaches 25% of the concentration of PFOA in the untreated water.

[0032] [Figure 4B]Figure 4B provides a plot of the floor volume equivalent as a function of the volume molasses value of the floor adsorbent when the concentration of PFOA in the water at the floor outlet port reaches 25% of the concentration of PFOA in the untreated water. [Modes for carrying out the invention]

[0033] This disclosure is not limited to the specific systems, apparatus, and methods described herein, as they may vary. The terms used in this description are intended to describe only specific versions or embodiments and are not intended to limit their scope.

[0034] As used in this document, the singular forms “a,” “an,” and “the” include multiple references unless explicitly indicated in the context. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Nothing in this disclosure should be construed as acknowledging that the embodiments described herein do not have prior rights to such disclosures by prior art. As used in this document, the term “including” means “including, but not limited to.”

[0035] As used herein, the term "approximately" means a number within plus or minus 10% of the number being modified. Therefore, approximately 50% means a range of 45% to 55%. When describing temperature, the term "approximately" refers to a given temperature within ±5 degrees.

[0036] As used herein, the term “adsorbent composition” means a material or mixture of materials containing an adsorbent. An adsorbent composition may be formed entirely from an adsorbent medium, or the adsorbent may contain one or more inert materials, fillers, binders, or other compositions that do not have any significant adsorbent capacity.

[0037] As used herein, the term “adsorbent medium” means all known materials from any source capable of adsorbing or absorbing liquids and / or gases. For example, adsorbent mediums may include, in non-limiting examples, one or more of the following: carbonaceous char, activated carbon, reactivated carbon, carbon nanotubes, graphene, natural and synthetic zeolites, silica, silica gel, alumina, polystyrene sulfonates, alumina, zirconia, and diatomaceous earth.

[0038] As used herein, the term “perfluoroalkyl and polyfluoroalkyl substances (PFAS)” means any perfluoroalkyl or polyfluoroalkyl substance, a mixture of such substances, or a derivative of one or more such substances. Examples of perfluoroalkyl and polyfluoroalkyl substances include perfluoroalkyl sulfonates, perfluoroalkanesulfonic acids (PFSA), N-butylperfluoroalkanesulfonamide (BuFASA), N-butylperfluoroalkanesulfonamideethanol (BuFASE), N-butylperfluoroalkanesulfonamideacetic acid (BuFASAA), N-ethylperfluoroalkanesulfonamide (EtFASA), N-ethylperfluoroalkanesulfonamideethanol (EtFASE), N-ethylperfluoroalkanesulfonamideacetic acid (EtFASAA), perfluoroalkanesulfonamide (FASA), and perfluoroalkanesulfonamideethanol. Examples include (FASE), perfluoroalkanesulfonamide acetate (FASAA), N-methylperfluoroalkanesulfonamide (MeFASA), N-ethylperfluoroalkanesulfonamide acetate (MeFASAA), N-methylperfluoroalkanesulfonamide ethanol (MeFASE), perfluoroalkanesulfonyl fluoride (PASF), fluoroprotein (FP), fluorotelomer carboxylic acid (FTCA), fluorotelomer alcohol (FTOH), fluorotelomer sulfonate (FTS), fluorotelomer sulfonic acid (FTSA), perfluoroalkyl acid (PFAA), perfluoroalkyl sulfonamide ethanol (PFOSE), and their derivatives. These include, for example, ammonium perfluorooctanoate (APFO), ammonium 4,8-dioxa-3H-perfluorononanoate, N-methylperfluorooctanesulfonamide (MeFOSA), perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid, perfluorooctanesulfonic acid (PFOS), ammonium 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoate, ammonium 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoate, 1,2,2,2-Tetrafluoroethyl ether, 4:2-Fluorotelomersulfonic acid (4:2 FtS), 6:2-Fluorotelomersulfonic acid (6:2 FtS), 8:2-Fluorotelomersulfonic acid (8:2 FtS), Perfluorobutanoic acid (PFBA), Perfluorobutanesulfonic acid, Perfluorobutanesulfonic acid (PFBS), Perfluorohexanesulfonic acid, Perfluorohexanesulfonic acid (PFHxS), Perfluorohexanoic acid, Perfluorohexanoic acid (PFHxA), 4,8-Dioxa-3H-perfluorononanoic acid, ammonium perfluorooctanoate (APFO), N-ethylperfluorooctanesulfonamide (EtFOSA), N-ethylperfluorooctanesulfonamide ethanol (EtFOSE), perfluorooctanesulfonamide (PFOSA), perfluorooctanesulfonamide acetate (FOSAA), perfluorooctanesulfonamide ethanol (FOSE), perfluorobutanoic acid, perfluorobutanoic acid, perfluorobutyric acid, perfluoroalkyl carboxylic acid, perfluoroalkyl carboxylic acid (PFCA), perfluorodecanoic acid, perfluorodecanoic acid (PFDA), perfluorododecanoic acid, perfluorododecanoic acid (PFDoA), perfluorododecanesulfonic acid (PFDoS), perfluorododecanesulfonic acid (PFDoSA), perfluorodecanesulfonic acid, perfluorodecanesulfonic acid (PFDS), Examples include perfluoroheptanoates, perfluoroheptanoic acid (PFHpA), perfluoroheptanesulfonic acid, perfluoroheptanesulfonic acid (PFHpS), perfluorononanoic acid, perfluorononanoic acid (PFNA), perfluorononanesulfonic acid, perfluorononanesulfonic acid (PFNS), perfluorooctanoic acid, perfluorophosphonic acid (PFPA), perfluoropentanoic acid, perfluoropentanesulfonic acid (PFPeA), perfluoropentanesulfonic acid, perfluoropentanesulfonic acid (PFPeS), perfluorophosphinic acid (PFPiA), perfluorotetradecanoic acid (PFTeDA), perfluorotridecanoic acid (PFTrDA), perfluoroundecanoic acid, perfluoroundecanoic acid (PFUnA), perfluoroundecanesulfonic acid (PFUnS), perfluoroundecanesulfonic acid (PFUnSA), and polytetrafluoroethylene (PTFE).

[0039] As used herein, “iodine value” or “IV” refers to either the gravimetric iodine value or the volumetric iodine value. Iodine value is a measure of the equilibrium mass of iodine adsorbed on the surface of a normalized amount of adsorbent. Iodine value is a measure of the surface area and porosity of the adsorbent.

[0040] When used herein, "gravimetric iodine value" or "IV" g "Iodine value" refers to the properties of adsorbents formed from carbonaceous materials, as determined by the industry standard test ASTM D4607-14. The gravimetric iodine value is reported in units of the mass of iodine adsorbed per unit mass of adsorbent.

[0041] When used herein, the term "volume iodine value" or "IV" is used. v The term "Iodine Value" refers to the product of the gravimetric iodine value and the apparent density of the adsorbent. The apparent density of the adsorbent is obtained by the industry standard test ASTM D2854-09 (2019). The gravimetric iodine value has the meaning described in the previous section. The volumetric iodine value is reported in units of the mass of iodine adsorbed per unit volume of adsorbent.

[0042] As used herein, “molasses value” or “MN” refers to either the weight molasses value or the volume molasses value. The molasses value is a measure of the decolorization ability of an adsorbent and an indicator of the micropore and transport pore structure of the adsorbent.

[0043] When used herein, "weight molasses value" or "MN" g This refers to the determination of the decolorization capacity of the adsorbent according to Calgon Carbon Method Number TM-3, titled "Determination of the Molasses Number of Activated Carbon." The complete test procedure is fully described herein. The gravimetric molasses number is reported as a unitless quantity measured per mass of the adsorbent.

[0044] When used herein, the term "volume molasses value" or "MV" is used. v The term "volume molasses value" refers to the product of the weight molasses value and the apparent density of the adsorbent. The weight molasses value has the meaning described in the previous section. The apparent density of the adsorbent is obtained by the industry standard test ASTM D2854-09 (2019). The volume molasses value is reported as a unitless quantity measured per volume of adsorbent.

[0045] Adsorbents and adsorbent compositions

[0046] This disclosure provides an adsorbent composition comprising at least one adsorbent effective for removing one or more perfluoroalkyl and polyfluoroalkyl substances from a fluid, as described above. The at least one adsorbent is present in an amount of at least about 450 mg / cm³. 3 (about 450mg / cm 3 ~about 600mg / cm 3 ) Volumetric iodine value, and at least about 100 cm -3 Volume molasses value (approximately 100 cm³) -3 ~about 400cm -3 ) indicates.

[0047] Advantageously, at least approximately 450 mg / cm³ 3 The volumetric iodine value and at least about 100 cm³ -3 Adsorbents having a volume molasses value of can exhibit excellent ability for adsorbing one or more perfluoroalkyl and polyfluoroalkyl substances. In one embodiment, one or more adsorbents are at least about 460 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 470 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 480 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 490 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 500 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 510 mg / cm³.3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 520 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 530 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 540 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 550 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 560 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 570 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In one embodiment, one or more adsorbents are at least about 580 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In any embodiment, one or more adsorbents are at least about 590 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In any embodiment, one or more adsorbents are present in a volume molasses value of at least about 600 mg / cm³. 3 The volumetric iodine value, and at least about 100 cm³ -3 This indicates the volume molasses value. In any embodiment, one or more adsorbents are approximately 450 mg / cm³. 3 ~about 500mg / cm 3 , about 470mg / cm 3 ~about 550mg / cm 3, about 500 mg / cm 3 ~ about 550 mg / cm 3 , about 520 mg / cm 3 ~ about 550 mg / cm 3 Or about 490 mg / cm 3 ~ about 520 mg / cm 3 Indicates the volumetric iodine value. The aforementioned values and ranges can be used alone or in combination, and any range may be formed by selecting two or more of the above endpoints.

[0048] In any embodiment, including those overlapping with the embodiments of the previous paragraph, the one or more adsorbents have a volume of about 100 cm -3 , about 110 cm -3 , about 120 cm -3 , about 130 cm -3 , about 140 cm -3 , about 150 cm -3 , about 160 cm -3 , about 170 cm -3 , about 180 cm -3 , about 190 cm -3 , about 200 cm -3 , about 210 cm -3 , about 220 cm -3 , about 230 cm -3 , about 240 cm -3 , about 250 cm -3 , about 260 cm -3 , about 270 cm -3 , about 280 cm -3 , about 290 cm -3 , about 300 cm -3 , about 310 cm -3 0, about 320 cm -3 , about 330 cm -3 , about 340 cm -3 , about 350 cm -3 , about 360 cm -3 , about 370 cm -3 , about 380 cm -3 , about 390 cm -3 , about 400 cm -3 Or indicates the volumetric molasses value of any range formed by selecting two or more of the above values as endpoints.

[0049] The apparent density of the adsorbent is, as disclosed herein, not limited to, and in any embodiment, about 1.00 g / cm³. 3 Less than approximately 0.95 g / cm³ 3 Less than approximately 0.90 g / cm³ 3 Less than approximately 0.85 g / cm³ 3 Less than approximately 0.80 g / cm³ 3 Less than approximately 0.75 g / cm³ 3 Less than approximately 0.70 g / cm³ 3 Less than approximately 0.65 g / cm³ 3 Less than approximately 0.60 g / cm³ 3 Less than approximately 0.55 g / cm³ 3 Less than approximately 0.50 g / cm³ 3 Less than approximately 0.45 g / cm³ 3 Less than approximately 0.40 g / cm³ 3 Less than or approximately 0.35 g / cm³ 3 It may be less than 1.00 g / cm³. In any embodiment, the apparent density of the adsorbent is about 1.00 g / cm³. 3 , about 0.95g / cm 3 , about 0.90g / cm 3 , about 0.85g / cm 3 , about 0.80g / cm 3 , about 0.75g / cm 3 , about 0.70g / cm 3 , about 0.65g / cm 3 , about 0.60g / cm 3 , about 0.55g / cm 3 , about 0.50g / cm 3 , about 0.45g / cm 3 , about 0.40g / cm 3 , about 0.35g / cm 3 , about 0.30g / cm 3 , or any range formed as an endpoint from any two of these values. In any embodiment, the apparent density of the adsorbent is about 0.30 g / cm³. 3 ~Approx. 1.00g / cm 3 , about 0.30g / cm 3 ~Approx. 0.95g / cm 3 , about 0.30g / cm 3 ~Approx. 0.90g / cm 3, about 0.30g / cm 3 ~Approx. 0.85g / cm 3 , about 0.30g / cm 3 ~about 0.80g / cm 3 , about 0.30g / cm 3 ~Approx. 0.75g / cm 3 , about 0.30g / cm 3 ~Approx. 0.70g / cm 3 , about 0.30g / cm 3 ~Approx. 0.65g / cm 3 , about 0.30g / cm 3 ~Approx. 0.60g / cm 3 , about 0.30g / cm 3 ~about 0.55g / cm 3 , about 0.30g / cm 3 ~about 0.50g / cm 3 , about 0.30g / cm 3 ~Approx. 0.45g / cm 3 , about 0.30g / cm 3 ~Approx. 0.40g / cm 3 Or approximately 0.30 g / cm³ 3 ~Approx. 0.35g / cm 3 That's fine.

[0050] The adsorbent composition may contain one or more adsorbents, each adsorbent comprising or derived from an adsorbent medium selected from (but not limited to) one or more of the following: carbonaceous char, activated carbon, carbon nanotubes, graphene, reactivated carbon, carbon black, natural and synthetic zeolites, silica, silica gel, alumina, alumina clay, zirconia, diatomaceous earth, and metal oxides. In any embodiment, an adsorbent composition comprising one or more adsorbents may comprise a single type of adsorbent medium, or may be combined with one or more additional types of adsorbent or non-adsorbent mediums or adsorbents derived therefrom. In embodiments in which the adsorbent composition comprises two or more adsorbents, the two or more adsorbents may be mixed together and may comprise or derived from the same or different precursor materials selected from those described above.

[0051] In any embodiment, one or more adsorbents may include activated carbon and / or reactivated carbon. In such embodiments, the activated carbon or reactivated carbon may be prepared from precursor carbonaceous materials selected from bituminous coal, subbituminous coal, lignite, brown coal, anthracite, wood, wood chips, sawdust, peat, nut shells, pits, coconut shells, babassu nuts, macadamia nuts, dendezza nuts, peach pits, cherry pits, olive pits, walnut shells, wood, lignin, polymers, nitrogen-containing polymers, resins, petroleum pitch, bagasse, rice husks, corn husks, wheat husks and rice husks, graphene, carbon nanotubes, polymer fibers, any other carbonaceous materials or any combination thereof. In any embodiment, the reactivated carbon may be derived from activated carbon of any origin that is depleted or substantially depleted from use.

[0052] The activated carbon and reactivated carbon suitable for use in the adsorbents and adsorbent compositions disclosed herein may be any grade or type selected based on performance requirements, cost, and / or other considerations. The activated carbon or reactivated carbon may be used in one or more of the following forms: powder form called “powdered activated carbon” or “PAC”, granular form called “granular activated carbon” or “GAC”, or pellet form called pelletized activated carbon. In any embodiment, the adsorbent may contain activated or reactivated carbon in one of the PAC, GAC, or pelletized forms, or may contain a mixture of two or more forms. Powdered activated carbon (PAC) is defined herein as particles that pass through an 80-mesh sieve (pores of about 0.180 mm). Granular activated carbon (GAC), as used herein, is defined as activated carbon particles of a size that can be held on a 50-mesh sieve (pores of about 0.300 mm). While these particle size ranges are mentioned for activated carbon adsorbents, it is also intended that any of the disclosed adsorbents may be measured by the 50-mesh and 80-mesh sieve sizes described above.

[0053] In any embodiment, the adsorbent composition contains at least about 450 mg / cm³ 3The volumetric iodine value and at least about 100 cm³ -3 An adsorbent having a volume molasses value may contain one or more additional components, for example, an additional adsorbent for removing one or more perfluoroalkyl and polyfluoroalkyl substances, an adsorbent for removing non-PFAS compounds, or a non-adsorbent. For example, in any embodiment, the adsorbent composition may contain at least two different adsorbent types, each effective in absorbing or adsorbing one or more perfluoroalkyl and polyfluoroalkyl substances. In any embodiment, the adsorbent composition described herein may further contain at least one compound that is not an adsorbent and is not substantially able to absorb or adsorb perfluoroalkyl and polyfluoroalkyl substances or any other compound.

[0054] For example, in any embodiment, the adsorbent composition contains at least about 450 mg / cm³ 3 The volumetric iodine value and at least about 100 cm³ -3 The composition may be formed comprising an adsorbent having a volume molasses value and a non-adsorbent that acts as a binder. Such a composition can be molded, extruded, or otherwise formed into one or more shapes such as pellets. The type of binder is not particularly limited and any organic or inorganic binder known in the art can be mentioned. Common examples of inorganic binders include metals, ceramics, clay, glass, or a combination of one or more of the above. Examples of organic binders include petroleum resins and / or pitch, natural resins and / or pitch, polymers, or a combination of one or more of the above.

[0055] In any embodiment, the present disclosure is at least about 450 mg / cm³ 3 The volumetric iodine value and at least about 100 cm³ -3 An adsorbent composition containing one or more adsorbents having a volume molasses value of 450 mg / cm³ may be provided in a container. 3 It has a volumetric iodine value of at least about 100 cm³ -3An adsorbent composition comprising one or more adsorbents having a volume molasses value is held, and is configured and sized to receive a fluid (i.e., liquid or gas) and to transport the fluid on or through the container, thereby bringing the adsorbent composition and the fluid into contact with the one or more adsorbents. The type of container is not particularly limited. For example, in any embodiment, the container may be a permanent container installed within an apparatus or process facility and connected by piping or other fluid conduits so that the liquid or gas flows through the container. From time to time, used adsorbents can be emptied from the container and replaced with either unused or reactivated adsorbents, or both, to ensure that it remains effective in removing perfluoroalkyl and polyfluoroalkyl substances, or chemically similar or chemically related compounds from the liquid or gas flowing through the container. The physical form of the adsorbent composition comprising one or more adsorbents provided in the container is not limited and may be provided loosely (by itself) or may be formed as a cartridge with other structural materials that hold it in place.

[0056] In another example, and in any embodiment, the container itself may be designed to be quickly replaced with minimal changes to external components such as pumps and conduits that transport the liquid or gas to the container. In such embodiments, the container may be referred to as a “cartridge” and can be connected to and disconnected from surrounding components. In any embodiment, the cartridge may be disposable, such as in consumer drinking water applications. Alternatively, in another example and in any embodiment, the cartridge may be intended to be returned to service after the completion of refurbishment work, with the used adsorbent cartridge being returned for cleaning or reactivation of the adsorbent and refilled with fresh, unused or reactivated adsorbent.

[0057] Manufacturing method

[0058] The adsorbent composition removes one or more perfluoroalkyl and polyfluoroalkyl substances, with a concentration of at least approximately 450 mg / cm³. 3 (For example, approximately 450 mg / cm³)3 ~about 600mg / cm 3 ) Volumetric iodine value and at least about 100 cm -3 (For example, about 100cm) -3 ~about 400cm -3 It contains one or more adsorbents that are effective in exhibiting the volume molasses value of ).

[0059] At least approximately 450 mg / cm³ 3 The volumetric iodine value and at least about 100 cm³ -3 One or more adsorbents having a volume molasses value may be formed from one or more precursor materials selected from, but not limited to, one or more of the following: carbonaceous char, activated carbon, carbon nanotubes, graphene, reactivated carbon, carbon black, natural and synthetic zeolites, silica, silica gel, alumina, alumina clay, zirconia, diatomaceous earth, and metal oxides. If the adsorbent contains activated carbon or reactivated carbon, the activated carbon and reactivated carbon may be of any grade or type, such as PAC, GAC, pelletized activated carbon, any reactivated form thereof, or any combination thereof.

[0060] Granular activated carbon or reactivated carbon can be formed by grinding a precursor carbonaceous material into a powder of a desired size. The powder may optionally be mixed with a binder. The finely ground material may optionally be formed into briquettes together with the binder, and then ground into granules of a desired size. The resulting granular material may be carbonized to remove volatile compounds and alter its properties, such as activating the precursor carbonaceous material.

[0061] Pelleted activated carbon can be formed by finely grinding a precursor carbonaceous material, binding the ground material with a binder, and extruding the mixture into pellets. The pellets may be carbonized to alter their properties, such as removing volatile compounds and activating the precursor carbonaceous material.

[0062] Adsorbents manufactured from activated carbon and / or reactivated carbon, as described above, have a final adsorbent product of at least about 450 mg / cm³. 3 The volumetric iodine value (for example, approximately 450 mg / cm³) 3 ~about 600mg / cm 3 ) and at least about 100 cm -3 (For example, about 100cm) -3 ~about 400cm -3 When the volume molasses value of ) is expressed, it can be formed by any method known in the art.

[0063] For example, activated carbon can be formed by oxidizing and deflorating unused carbonaceous material with steam and / or carbon dioxide to gasify it, thereby forming a desired pore structure in the activated carbon and providing desired material properties (e.g., gravimetric iodine value, gravimetric molasses value). In any embodiment, the initial oxidation and defloration steps may include chemical treatment with dehydrating chemicals, such as phosphoric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, or any combination thereof.

[0064] In another example, suitable activated carbon can be formed by a direct activation process. Such activated carbon adsorbents are sometimes called direct activated carbon. In the direct activation process, a precursor carbonaceous material, usually coal, is crushed and sizing. The crushed and sizing precursor carbonaceous material is then carbonized and thermally activated.

[0065] In any embodiment, the suitable adsorbent may include a reactivated adsorbent whose adsorption capacity has been previously exhausted or substantially exhausted and which has been reactivated to restore at least a portion of its original adsorption capacity. Any of the adsorbents listed above can be reactivated after depletion, and reactivation can be carried out by heat, pressure, chemical exposure, or any combination thereof. In any embodiment, the reactivated adsorbent may include reactivated carbon. Reactivated carbon can be produced by heating depleted activated carbon in a low-oxygen atmosphere using steam as a selective oxidizer. During reactivation, absorbed and adsorbed organic compounds can volatilize from the activated carbon or be thermally decomposed to form carbon char. Heating is carried out at temperatures above about 500°C (e.g., about 500°C to about 1100°C), more specifically, at temperatures above about 700°C (e.g., about 700°C to about 1100°C), and the resulting reactivated carbon can then be reused for a variety of purposes, including water treatment.

[0066] Any step contains at least approximately 450 mg / cm³ 3 (For example, approximately 450 mg / cm³) 3 ~about 600mg / cm 3 Adsorbent having a volume iodine value of ) and at least about 100 cm -3 (For example, about 100cm) -3 ~about 400cm -3While it may be used to obtain an adsorbent having a volumetric molasses value of ), the following observations may provide useful guidelines to those skilled in the art, and the volumetric iodine value and volumetric molasses value of a particular adsorbent are influenced by many factors, including the selection of one or more precursor carbonaceous materials and the processing steps performed on the precursor carbonaceous materials. For example, in general, continuous steam activation of a precursor carbonaceous material generally increases the gravimetric iodine value and gravimetric molasses value, but at the same time decreases the apparent density of the carbonaceous material. Many precursor carbonaceous materials have a maximum gravimetric molasses value that can be achieved before further activation reduces the gravimetric molasses value. Therefore, simply increasing the gravimetric iodine value and gravimetric molasses value may not result in an increase in volumetric iodine value and volumetric molasses value beyond a certain point. To summarize all of the above, this disclosure describes an adsorbent that maximizes both volumetric iodine value and volumetric molasses value to achieve superior performance.

[0067] The adsorbents of this disclosure are primarily disclosed for the removal of perfluoroalkyl and polyfluoroalkyl substances, or chemically similar or related compounds, but the use of the adsorbents is not so limited. In further embodiments, the adsorbents are suitable for removing any compounds and / or by-products that cause taste and odor problems in water. Such compounds are referred to throughout the application as “taste and odor compounds.” Examples of such taste and odor compounds include trans-1,10-dimethyl-trans-9-decalol (“diosmin”), 2-methylisoborneol (MIB), isopropylmethoxypyrazine (IPMP), isobutylmethoxypyrazine (IBMP), methyl tert-butyl ether (MTBE), 2,4-heptadienal, decandinal, octanal, chlorine, chloramine, chlorophenol, iodoform, hydrocarbons, and one or more volatile organic compounds (VOCs).

[0068] As described herein, the surface and pore morphology of the adsorbent is described by a combination of volume iodine value and volume molasses value. While we do not wish to be bound by theory, the combination of volume iodine value and volume molasses value together describes the overall adsorption capacity of the adsorbent and the types of molecules that the adsorbent is effective at adsorbing. After intensive experiments, the applicant determined that the adsorbent has a volume of at least about 450 mg / cm³. 3 The volumetric iodine value (for example, approximately 450 mg / cm³) 3 ~about 600mg / cm 3 ) and at least about 100 cm -3 (For example, about 100cm) -3 ~about 400cm -3 The applicant determined that adsorbents having only one of the volumetric molasses values ​​cannot meet the requirements for excellent adsorption / absorption capacity of a wide range of perfluoroalkyl and polyfluoroalkyl substances. Similarly, materials with a very high measurement of either the gravimetric iodine value or the gravimetric molasses value cannot compensate for a decrease in the other measurement. The applicant also determined that volumetric measurement, not gravimetric measurement, best represents the performance of adsorbents with respect to perfluoroalkyl and polyfluoroalkyl substances, and therefore apparent density is equally important in providing effective adsorbent compositions and adsorbents for the removal of perfluoroalkyl and polyfluoroalkyl substances from fluids.

[0069] How to use

[0070] Advantageously, the adsorbent formed by the method described herein contains at least about 450 mg / cm³ 3 (For example, approximately 450 mg / cm³) 3 ~about 600mg / cm 3 It has a volumetric iodine value of ) and at least about 100 cm³ -3 (For example, about 100cm) -3 ~about 400cm -3 It has a volumetric molasses value and exhibits excellent performance in removing one or more perfluoroalkyl and polyfluoroalkyl substances from fluids such as water (e.g., drinking water).

[0071] Provided herein is a method for removing one or more perfluoroalkyl and polyfluoroalkyl substances from a fluid, the method comprising contacting an adsorbent composition containing one or more adsorbents, as disclosed herein, with a fluid containing one or more perfluoroalkyl compounds and polyfluoroalkyl substances. As mentioned above, at least one adsorbent is at least about 450 mg / cm³ 3 (about 450mg / cm 3 ~about 600mg / cm 3 ) Volumetric iodine value, and at least about 100 cm -3 Volume molasses value (approximately 100 cm³) -3 ~about 400cm -3 ) indicates.

[0072] The method of contact is not particularly limited. For example, in any embodiment, a flow containing a fluid may pass through or over a floor containing an adsorbent composition containing one or more adsorbents. In another example, the adsorbent composition containing one or more adsorbents may be injected into the fluid or otherwise combined with the fluid. Optionally, the adsorbent composition containing one or more adsorbents may be collected from the fluid after adsorbing a desired amount of one or more perfluoroalkyl and polyfluoroalkyl substances from the fluid, for example, by filtering the fluid to isolate the adsorbent composition. The composition of the fluid is not limited and in any embodiment may include one or more of liquid water, water vapor, air, and soil. [Examples]

[0073] Before describing the examples, the test method must be fully described.

[0074] Determination of iodine value (IV)

[0075] The gravimetric iodine value of activated carbon samples was measured in accordance with ASTM D4607-14. The gravimetric iodine value is reported in milligrams, representing the amount of iodine adsorbed per gram of activated carbon sample.

[0076] To calculate the volumetric iodine value, the apparent density (ρ) of the activated carbon sample is used. b The iodine value was measured according to the industry standard test ASTM D2854-09 (2019). After determining the gravimetric iodine value and apparent density, the volumetric iodine value was determined by multiplying the gravimetric iodine value by the apparent density. Therefore, the volumetric iodine value is reported in milligrams per cubic centimeter.

[0077] Weight molasses value (MN) g ) decision

[0078] To determine the gravimetric molasses value, we used Calgon Carbon Corporation's test method number TM-3 ("TM-3"). TM-3 is intended to determine the decolorization capacity of activated carbon. The decolorization capacity of activated carbon represents the pore structure and material transport of the activated carbon. Determination of gravimetric molasses value according to TM-3. Volumetric molasses value (MN) v The molasses value was calculated by multiplying the molasses value of TM-3 by the apparent density obtained by ASTM D2854-09 (2019). The weight molasses value was determined by TM-3 as follows:

[0079] Restrictions: The concentration of the molasses solution used in the test depends on the standard carbon. Where used herein, “standard carbon” refers to the activated carbon adsorbent, which is the reference substance for the properties of the weight molasses value. As will be understood by those skilled in the art, “200 standard carbon” is expected to yield a weight molasses value of 200, and “250 standard carbon” is expected to have a weight molasses value of 250. 200 standard carbon should be used for activated carbon products expected to have a weight molasses value of less than 230. 250 standard carbon should be used for activated carbon products expected to have a weight molasses value of less than 350. 400 standard carbon should be used for activated carbon products expected to have a weight molasses value of 350 or more. Whenever a product has a molasses specification range that includes a molasses standard carbon limit, a higher molasses standard carbon should be used. In such cases, it is appropriate to include the molasses standard carbon to be used in the product specification as a manufacturing note. Molasses solutions cannot be diluted. A fixed path length of 2.5 mm must be used.

[0080] As those skilled in the art will understand, standard carbon is not limited insofar as it is a suitable standard material for molasses number. An example of 400 standard carbon is "RB," available from Calgon Carbon Corporation in Moon Township, Pennsylvania. RB is a powdered steam-activated carbon made from bituminous coal with a minimum weight iodine number of 1070 mg / g, a weight molasses number of 400, a maximum ash content of 23 mass%, a maximum moisture content of 2 mass%, and 60-75 mass% of particles screened at 325 mesh, or a size of less than 44 μm. A second example of 320 standard carbon is "RC," available from Calgon Carbon Corporation in Moon Township, Pennsylvania. RC is a powdered steam-activated carbon made from bituminous coal with a minimum weight iodine value of 1020 mg / g, a weight molasses value of 320, a maximum ash content of 23% by mass, a maximum moisture content of 2% by mass, and 60-75% by mass of particles screened at 325 mesh, or a size of less than 44 μm. A third example of 230 standard carbon is "BL," available from Calgon Carbon Corporation in Moon Township, Pennsylvania. BL is a powdered steam-activated carbon made from bituminous coal with a minimum weight iodine value of 1000 mg / g, a weight molasses value of 230, a maximum ash content of 10% by mass, a maximum moisture content of 2% by mass, and 60-75% by mass of particles screened at 325 mesh, or a size of less than 44 μm.

[0081] Method Principle: A solution of molasses is treated with a standard carbon having a known molasses value ("molasses standard carbon"), filtered, and the filtrate is analyzed by UV-vis spectrophotometric analysis to generate a relationship between molasses value and absorbance. Next, a solution of molasses is treated with a sample of carbon with decolorizing ability / unknown molasses value (e.g., adsorbents provided herein), filtered, and the filtrate is analyzed in the same manner. The higher the ability of the adsorbent to decolorize (i.e., decolorize) the molasses composition, the brighter the filtrate and, conversely, the lower the absorbance. Therefore, a higher molasses value corresponds to a higher decolorizing ability, as shown in Figure 1. The absorbance of each filtrate is determined using a standard spectrophotometer with a path length of 2.5 mm and a wavelength of 472 nm (Figure 2 shows the transmittance spectrum of a typical filtrate). The molasses value of each sample is calculated from the ratio of the absorbance value of the sample to the standard carbon: Molasses value = (A × B) / C In the formula, A is the molasses value of a standard carbon having a known molasses value, B is the average absorbance of three measurements of the standard carbon having a known molasses value, and C is the absorbance of the filtrate of the adsorbent being analyzed (i.e., having an unknown molasses value).

[0082] Safety Precautions: When handling experimental equipment, careful handling and excellent experimental techniques must always be used. Personnel conducting this test must be aware of potential safety issues associated with the equipment used in this procedure.

[0083] The equipment used in TM-3 is listed in Table 1 below. [Table 1]

[0084] The reagents used in TM-3 are listed in Table 2 below. [Table 2]

[0085] A molasses molasses solution ("standardized molasses solution") for determining the molasses value was prepared according to the following procedure: 1. Weigh approximately 50 grams of molasses into a clean, dry beaker and leave it until the water is heated to 95°C. 2. Using a graduated cylinder, 1000 mL of ASTM Type 2 water was added to a stainless steel beaker. 3. Cover the beaker with aluminum foil or a large glass cover, place it on a hot plate, and heat it to 95°C. 4. Once the water reached 95°C, the weighed molasses was transferred to a stainless steel beaker and mixed thoroughly. The stainless steel beaker was then removed from the hot plate. 5. The solution was cooled to room temperature (approximately 25°C). 6. The molasses solution was drawn up from the stainless steel beaker into a suitable container. A portion of the TYGON tubing was placed in the beaker, with the end of the tubing 1 inch above the bottom of the beaker. A pipette bulb was used to start the siphon. The solution was siphoned into another container (e.g., a large glass bottle). 7. Discard the remaining contents of the beaker. Store the molasses solution in the refrigerator for up to 24 hours. Keep the molasses solution on ice while performing the test method. 8.0.46 ± 0.0002 grams of 250 molasses standard carbon were weighed into a clean, dry 400 mL beaker. 9.50 mL of molasses solution was pipetteed into a beaker. The beaker was swirled while adding the molasses solution until the 250 molasses standard carbon was completely wet. 10. Place the beaker on a hot plate and position the thermocouple / thermometer inside the beaker so that its tip is at the bottom. Heat the solution until the thermocouple / thermometer reaches 98°C and start the stopwatch. Remove the thermocouple or thermometer and boil the solution for 30 seconds. 11. The sample was vacuum filtered through a Buchner funnel using pre-prepared WHATMAN® No.3 filter paper. The filter was covered with approximately 20 mL of solution, and this filtrate was discarded. The remaining portion was filtered. 12. The absorbance of the filtrate at a wavelength of 472 nm was measured and recorded using the instrument parameters specified above. The filtrate was considered standardized if its absorbance was between 0.630 and 0.650 ("Standardized 250 filtrate"). 13. If the absorbance was greater than 0.650, the filtrate was considered too dark. In such cases, water could be added to the molasses solution. To determine the amount of water needed, the amount of remaining molasses solution was measured, multiplied by 0.640, and then multiplied by the absorbance recorded from step 12. This value was subtracted from the total amount of molasses solution to obtain the amount of water needed to be added to the molasses solution. The water was added and the solution was thoroughly mixed. Steps 8-13 were repeated until three consecutive analyte samples had absorbance values ​​between 0.630 and 0.650 (472 nm). 14. If the measured absorbance was less than 0.630, the filtrate was considered too bright. In such cases, more molasses can be added to the molasses solution. To determine the amount of molasses to add, the volume of the molasses solution was measured, multiplied by 0.640, and then multiplied by the absorbance recorded from step 12. This value was subtracted from the total volume of the molasses solution by 10, and this result represents the amount (by weight) of molasses that needs to be added to the molasses solution. The required amount of molasses was added to a small glass beaker. Approximately 25 mL of molasses solution was added to the beaker to dissolve the molasses. The beaker was heated on a hot plate to 90°C and then allowed to cool slightly. The contents were added to the molasses solution and mixed well. Steps 8-14 were repeated until three consecutive samples had absorbance values ​​(472 nm) between 0.630 and 0.650.

[0086] 400 Standard Carbon Standardization 15.0.46 ± 0.0002 grams of 400 molasses standard carbon were weighed into a clean, dry 400 mL beaker. 16.50 mL of molasses solution was pipetteed into a beaker. The beaker was swirled while adding the molasses solution until the carbon was completely wet. 17. Place the beaker on a hot plate and position the thermocouple / thermometer inside the beaker so that its tip is at the bottom. Heat the solution until the thermocouple / thermometer reaches 98°C and start the stopwatch. Remove the thermocouple or thermometer and boil the solution for 30 seconds. 18. The sample was vacuum filtered through a Buchner funnel using pre-prepared WHATMAN® No.3 filter paper. The filter was covered with approximately 20 mL of solution, and this filtrate was discarded. The remaining 30 mL was filtered, and the filtrate was used for subsequent measurements. 19. The absorbance of the filtrate at a wavelength of 472 nm was measured and recorded using a 2.5 mm fixed path cell. The filtrate was considered normalized if the measured absorbance was between 0.390 and 0.410. 20. If the absorbance was greater than 0.410, the filtrate was considered too dark. In such cases, water could be added to the molasses solution. To determine the amount of water needed, the amount of remaining molasses solution was measured, multiplied by 0.400, and then multiplied by the absorbance recorded from step 19. This value was subtracted from the total amount of molasses solution to obtain the amount of water needed to be added to the molasses solution. The water was added and the solution was thoroughly mixed. Steps 8-13 were repeated until three consecutive analyte samples had absorbance values ​​between 0.390 and 0.410 (at 472 nm). 21. If the absorbance was less than 0.390, the filtrate was considered too bright. In such cases, more molasses can be added to the molasses solution. To determine the amount of molasses to add, the volume of the molasses solution was measured, multiplied by 0.640, and then multiplied by the absorbance recorded from step 19. This value was subtracted from the total volume of the molasses solution by 10, and this result represents the amount (by weight) of molasses that needs to be added to the molasses solution. The required amount of molasses was added to a small glass beaker. Approximately 25 mL of molasses solution was added to the beaker to dissolve the molasses. The beaker was heated on a hot plate to 90°C and then allowed to cool slightly. The contents were added to the molasses solution and mixed well. Steps 15-21 were repeated until three consecutive samples with absorbance values ​​(at 472 nm) were obtained, thereby obtaining a standardized molasses solution for subsequent use.

[0087] Sample analysis

[0088] The samples were analyzed according to the following procedure. 1. A sample of carbon with an unknown molasses value was provided and ground until more than 95% passed through a 325-mesh screen. If the sample was not from a recent production, it was dried to a constant weight at 150°C before use. A standard carbon internal carbon standard was prepared similarly. To ensure that the fineness of the materials was equivalent, equivalent amounts were finely ground. 2. A 0.46 ± 0.0002 gram portion of the dried, finely ground carbon sample was weighed into separate, clean, dry 400 mL beakers. 3. A filtration setup was prepared for filtering the sample. A WHATMAN® No.3 filter circle was placed in a Buchner funnel. The funnel was connected to a 250 mL filtration flask, and filtration vacuum was started. 50 mL of filter paper suspension was added, ensuring that the entire surface of the filter paper circle was coated. After all the liquid had been drained, the filtrate collected in the suction bottle was discarded. 4.50 mL of standardized molasses solution was pipetteed into a beaker containing the carbon to be analyzed. The beaker was swirled while adding the standardized molasses solution until the carbon was completely wetted. 5. Place the beaker on a hot plate and position the thermocouple or thermometer inside the beaker so that the tip is at the bottom of the beaker. Heat the solution until the thermocouple reads 98°C and start the stopwatch. Remove the thermocouple or thermometer and boil the solution for 30 seconds. 6. The sample was filtered by vacuum through a Buchner funnel using WHATMAN® No.3 filter paper, which had been prepared in accordance with Step 3. The filter was covered with approximately 20 mL of sample, and this filtrate was discarded. The remaining portion was filtered. 7.2.5 mm fixed-path KLETT® Summerson Cell was used to measure and record the absorbance of the filtrate at a wavelength of 472 nm. Deionized water or distilled water was used as the reference. 8. The molasses value was calculated: Molasses value = (A × B) / C In the formula, A is the molasses number of the standard carbon (250 or otherwise); B is the average absorbance of three determined values ​​of 250 standard carbon or other standard carbons; and C is the absorbance of the filtrate of the activated carbon being analyzed. 9. Molasses values ​​were reported to the nearest 10 increments using conventional rounding techniques. (e.g., 226 = 230)

[0089] Example 1

[0090] For Example 1, a sample of 12x40 granular activated carbon for use in a fixed or moving bed for the purification and decolorization of aqueous and organic liquids was prepared. The sample was obtained by re-aggregating activated carbon formed from bituminous coal. The bituminous coal was first finely ground into a powder, and then a binder was added to the powder. The powder and binder were then re-aggregated into briquettes. Following briquetting, the briquettes were ground and sized. Sizing was maintained to preserve particle sizes between 12 mesh (1.70 mm hole size) and 40 mesh (0.425 mm hole size). Note that the mesh size is US mesh size as described herein. The average particle diameter of the sample batch was 0.9 mm to 1.1 mm, and the amount of granular activated carbon with a particle size greater than 12 mesh (1.70 mm) was 5.0% by weight or less. The amount of granular activated carbon with a particle size less than 40 mesh (0.425 mm) was 4% by mass or less. The crushed and sizing particles were carbonized and then thermally activated. After thermal activation, the granular activated carbon of Example 1 had a moisture content of less than 2% by mass as measured by ASTM D2867, an abrasion count of 75 as measured by AWWA B604, and an apparent density of 0.49 g / cm³ as measured by ASTM D2854-09. 3 That was the case.

[0091] Example 2

[0092] The re-aggregated granular activated carbon sample yielded a product of 0.42 g / cm³. 3 It was prepared in the same manner as described in Example 1, except that the activation was carried out to have an apparent density.

[0093] Example 3

[0094] The re-aggregated granular activated carbon sample yielded a product of 0.38 g / cm³. 3 It was prepared in the same manner as described in Example 1, except that the activation was carried out to have an apparent density.

[0095] Comparative Example 1 (C1)

[0096] A sample of granular activated carbon for Comparative Example 1 was prepared. In Comparative Example 1, the sample was activated carbon formed from coconut shells. The coconut shells were first treated by slowly thermally decomposing them to form charcoal. Sizing was performed according to ASTM D2862-16, retaining only particle sizes between 12 mesh (1.70 mm hole size) and 40 mesh (0.425 mm hole size). The amount of granular activated carbon with a particle size of less than 12 mesh (1.70 mm) was 5% by mass or less. The amount of granular activated carbon with a particle size of less than 40 mesh (0.425 mm) was 4% by mass or less. The sized particles were then thermally activated. The hardness of the obtained granular activated carbon was at least 95, as measured by ASTM D3802. The apparent density of the obtained granular activated carbon, as measured by ASTM D2854, was 0.48 g / cm³. 3 That was the case.

[0097] Comparative Example 2 (C2)

[0098] A sample of granular activated carbon for Comparative Example 2 was prepared. In Comparative Example 2, the sample was obtained by re-aggregating activated carbon formed from bituminous coal. The bituminous coal was first finely ground into a powder, and then a binder was added to the powder. The powder and binder were then re-aggregated into briquettes. Following briquetting, the briquettes were crushed and sized. Sizing was performed according to ASTM D2862-16, maintaining only particle sizes between 12 mesh (1.70 mm hole size) and 40 mesh (0.425 mm hole size). The amount of particles with a particle size greater than 12 mesh (1.70 mm) was 5% by mass or less. The amount of particles with a particle size greater than 40 mesh (0.425 mm) was 4% by mass or less. The crushed and sized briquettes were then carbonized and then thermally activated. The hardness number measured by ASTM D3802 was at least 75. The apparent density measured by ASTM D2854 was 0.54 g / cm³. 3 That was the case.

[0099] Comparative Example 3 (C3)

[0100] Samples prepared from commercially available lignite-based granular activated carbon were also tested. HYDRODARCO 4000 is a lignite-based granular activated carbon that was sized according to ASTM D2862-16 and retained only particle sizes between 12 mesh (hole size of 1.70 mm) and 40 mesh (hole size of 0.425 mm). The amount of granular activated carbon with a particle size less than 12 mesh (1.70 mm) was 5% by mass or less. The amount of granular activated carbon with a particle size less than 40 mesh (0.425 mm) was 4% by mass or less.

[0101] Comparative Example 4 (C4)

[0102] Samples prepared from commercially available lignite-based granular activated carbon were tested. The activated carbon of Comparative Example 4 is granular activated carbon formed by directly activating bituminous coal.

[0103] Results

[0104] For Examples 1 to 3 and Comparative Examples 1 to 4, the removal effects of specific perfluoroalkyl and polyfluoroalkyl substances were tested. Six beds consisting only of the activated carbon of each of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared according to ASTM D6586. The test was carried out according to the EPA Method 537 Version 1.1 methodology for measuring the adsorption of contaminants in aqueous systems onto granular activated carbon by the Rapid Small Scale Column Test (RSSCT) prepared as described above. The feed water passed through the bed, and the concentrations of perfluoroalkyl and polyfluoroalkyl substances at the outlet were measured at specified intervals. To normalize the bed size, the results were reported in terms of "bed volume", which is the volume of water passed through the activated carbon bed divided by the volume of the bed itself. During the test, it was pointed out that the point at which 25% of the concentration of perfluoroalkyl and polyfluoroalkyl substances "broke through" the activated carbon bed. For a specific adsorbent, a higher bed volume at 25% breakthrough means that the same amount of adsorbent adsorbed more perfluoroalkyl and polyfluoroalkyl substances and was thus more effective.

[0105] In the results, PFOA is perfluorooctanoic acid (also known by IUPAC nomenclature pentadecafluorooctanoic acid or simply C8). Examples 1-3 and Comparative Examples 1-4 tested the amount of water that could pass through the activated carbon bed before at least 25% of the concentration of the contaminant PFOA "penetrated" the activated carbon bed, i.e., before it was detected in the filtered water. The results are shown in Table 3 below. Examples 1-3 and Comparative Examples 1-3 also tested the amount of water that could pass through the activated carbon bed before at least 25% of the concentration of the contaminant 4:2 FtS "penetrated" the activated carbon bed. 4:2 FtS is 4:2 fluorotelomer sulfonic acid, a perfluoroalkyl and polyfluoroalkyl substance, and is difficult to adsorb due to its low molecular weight. Based on the tests of Examples 1-3 and Comparative Examples C1-C4, the following results were obtained. TIFF0007897835000003.tif75157

[0106] The results are also shown in Figures 3, 4A, and 4B. Figure 3 plots the normalized concentration of PFOA measured in the column wastewater against the volume of water passing through the activated carbon adsorbent bed. In these experiments, the incoming water was present in concentration. The horizontal line corresponds to 25% of the initial concentration of PFOA measured at the outlet port of the activated carbon adsorbent bed. Therefore, in Figure 3, the larger the portion of the plotted curve below the horizontal line, the better the performance.

[0107] Figure 4A plots the number of floor volumes on the x-axis until 25% of PFOA breaks through the activated carbon adsorbent floor. As previously mentioned, PFOA concentration was present in the incoming water. Each vertical pair of data points represents a single experimental test. For example, the dotted vertical line represents a single material that was tested and showed a 25% PFOA breakthrough in approximately 10,000 floor volumes. The volume molasses value of that material was approximately 160 cm³. -3 (Represented by a square intersecting a vertical line), and the volumetric iodine value is approximately 250 mg / cm³. 3 (Represented by a diamond intersecting a vertical line). Optimal lines are provided for both the volumetric iodine value and volumetric molasses value corresponding to each sample.

[0108] Figure 4B plots the bed volume equivalent at 25% PFOA, measured at the bed exit port, as a function of the sample's volume molasses value. Each sample is similar to that shown in Figure 4A. Two correlations were also found. First, an overall correlation was performed for all data points, and R 2 The value was 0.8968. This indicates a low degree of fit. However, the inventors also noted that the volumetric iodine value was approximately 450 mg / cm³. 3 If the volume molasses value is less than approximately 100 cm³, the volume molasses value is approximately 100 cm³. -3 If a second correlation is performed on all data points except those less than R, 2 The value improved to 0.9928, indicating excellent fit.

Claims

1. An adsorbent for removing one or more perfluoroalkyl and polyfluoroalkyl substances (PFAS) from a fluid, comprising activated carbon, reactivated carbon, or a combination thereof, wherein the activated carbon, reactivated carbon, or combination thereof is re-aggregated. The adsorbent is 500 mg / cm³ ３ ~600 mg / cm³ ３ The volumetric iodine value, and 112 cm³ －３ ~400 －３ It has a volume molasses value, The bed containing the adsorbent removes perfluorooctanoic acid from at least 20,000 bed volumes of water containing perfluorooctanoic acid at a concentration of 61 ng / L or less, thereby enabling the generation of a filtered water stream before perfluorooctanoic acid at a concentration of 15 ng / L is detected in the filtered water stream. Adsorbent.

2. The volumetric iodine value is 500 mg / cm³. ３ ~550 mg / cm³ ３ The volume molasses value is 150 cm³. －３ ~350cm －３ The adsorbent according to claim 1.

3. The adsorbent according to claim 1, wherein the activated carbon or reactivated carbon is formed from a precursor carbonaceous material selected from one or more of the following: bituminous coal, subbituminous coal, lignite, brown coal, anthracite, wood, wood chips, sawdust, peat, nut shells, pits, coconut shells, babassu nuts, macadamia nuts, dendezza nuts, peach pits, cherry pits, olive pits, walnut shells, wood, lignin, polymers, nitrogen-containing polymers, resins, petroleum pitch, bagasse, rice husks, corn husks, wheat husks and rice husks, graphene, carbon nanotubes, and polymer fibers.

4. The adsorbent according to claim 1, wherein the activated carbon or reactivated carbon is formed from one or both bituminous carbon and subbituminous carbon.

5. A method for removing one or more perfluoroalkyl and polyfluoroalkyl substances from a fluid, wherein the method is: An adsorbent comprising activated carbon, reactivated carbon, or a combination thereof, wherein the activated carbon, reactivated carbon, or a combination thereof is re-aggregated, and having an iodine value of 500 mg / cm ３ to 600 mg / cm ３ and a molasses value of 112 cm －３ to 400 cm －３ ; and a step of preparing an adsorbent, and also A step of bringing the fluid into contact with the adsorbent, Includes, The bed containing the adsorbent removes perfluorooctanoic acid from at least 20,000 bed volumes of water containing perfluorooctanoic acid at a concentration of 61 ng / L or less, thereby enabling the generation of a filtered water stream before perfluorooctanoic acid at a concentration of 15 ng / L is detected in the filtered water stream. method.

6. The method according to claim 5, wherein the activated carbon or reactivated carbon is formed from a precursor carbonaceous material selected from one or more of the following: bituminous coal, subbituminous coal, lignite, brown coal, anthracite, wood, wood chips, sawdust, peat, nut shells, pits, coconut shells, babassu nuts, macadamia nuts, dendezza nuts, peach pits, cherry pits, olive pits, walnut shells, wood, lignin, polymers, nitrogen-containing polymers, resins, petroleum pitch, bagasse, rice husks, corn husks, wheat husks and rice husks, graphene, carbon nanotubes, and polymer fibers.

7. The method according to claim 6, wherein the activated carbon or reactivated carbon is formed from one or more bituminous carbon and subbituminous carbon.

8. The adsorbent is 500 mg / cm³ ３ ~550 mg / cm³ ３ It has a volumetric iodine value of 112 cm³. －３ ~350cm －３ The method according to claim 5, having a volume molasses value.

9. 500 mg / cm² ３ ~600 mg / cm³ ３ The volumetric iodine value and 112 cm³ －３ ~400 －３ An adsorbent composition comprising one or more adsorbents having a volume molasses value of, The aforementioned one or more adsorbents include re-aggregated activated carbon, re-aggregated re-activated carbon, or a combination thereof, The bed containing the adsorbent removes PFOA from at least 20,000 bed volumes of water containing PFOA at a concentration of 61 ng / L or less, thereby enabling the generation of filtered water before a concentration of PFOA of 15 ng / L is detected in the filtered water stream. Adsorbent composition.

10. The adsorbent composition according to claim 9, further comprising one or more inert materials, fillers, binders, or other compositions that do not have any significant adsorbent capacity.

11. The volumetric iodine value is 500 mg / cm³. ３ ~550 mg / cm³ ３ The volume molasses value is 150 cm³. －３ ~350cm －３ The adsorbent composition according to claim 9 or 10.

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