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WO2024186878A2 - Systèmes et procédés d'analyse de fluor organique total - Google Patents

Systèmes et procédés d'analyse de fluor organique total Download PDF

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Publication number
WO2024186878A2
WO2024186878A2 PCT/US2024/018635 US2024018635W WO2024186878A2 WO 2024186878 A2 WO2024186878 A2 WO 2024186878A2 US 2024018635 W US2024018635 W US 2024018635W WO 2024186878 A2 WO2024186878 A2 WO 2024186878A2
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WO
WIPO (PCT)
Prior art keywords
reactor
sample
less
organofluorine
exemplary
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PCT/US2024/018635
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English (en)
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WO2024186878A3 (fr
Inventor
Patrick Lee Ferguson
Marc Arnold Deshusses
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Duke University
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Publication of WO2024186878A2 publication Critical patent/WO2024186878A2/fr
Publication of WO2024186878A3 publication Critical patent/WO2024186878A3/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples

Definitions

  • the present disclosure relates to systems and methods for analyzing a sample comprising organofluorine material.
  • Organofluorine materials include compounds such as poly- and per-fluoroalkyl substances (PFAS) and are predominantly fluorinated anionic surfactants having straight chain or branched alkyl groups.
  • PFAS poly- and per-fluoroalkyl substances
  • the class of poly- and per-fluoroalkyl substances (PFAS) have unique properties such as, but not limited to, chemical stability, water, oil and grease repellence, resistance to heat and hydrophobicity. Because of poly- and per-fluoroalkyl substances’ (PFAS) unique chemical properties and stability in the environment and in higher organisms, they are ubiquitously known as persistent or forever chemicals. Currently, more regulatory attention is being diverted to poly- and per-fluoroalkyl substances (PFAS) and their remediation from environments.
  • a method of analyzing a sample comprising organofluorine material may comprise: providing a first reactor input to a first reactor with a high-pressure liquid stream, the first reactor input comprising the sample; in the first reactor, heating the first reactor input to a supercritical temperature and pressure; cooling an output stream from the first reactor to a subcritical temperature; adjusting a pressure of the cooled first reactor output to a subcritical pressure; mixing the decompressed cooled first reactor output with an indicator compound to generate an indicator mixture; providing the indicator mixture to a second reactor; heating the indicator mixture in the second reactor, thereby causing a reaction of the indicator compound with a fluorine-containing species and generating a second reactor output; providing the second reactor output to an analysis unit; and with the analysis unit, determining an amount of organofluorine material present in the sample.
  • An exemplary system may comprise: a sample preparation unit in fluid communication with a high-pressure liquid source and a sample source; a first reactor comprising a first reactor inlet and a first reactor outlet, the first reactor inlet being in fluid communication with the sample preparation unit, and the first reactor configured to heat a first reactor input to a supercritical temperature and pressure; a cooling unit in fluid communication with the first reactor output; a pressure regulator unit in fluid communication with an output stream from the cooling unit; a mixing unit in fluid communication with the pressure regulator unit and in fluid communication with an indicator compound source; a second reactor comprising a second reactor inlet and a second reactor outlet, the second reactor inlet being in fluid communication with the mixing unit, and the second reactor configured to heat a second reactor input to a reaction temperature; and an analysis unit in fluid communication with the second reactor outlet, configured to determine an amount of organofluorine material present in the sample.
  • FIG 1 shows a block diagram of an exemplary total organic fluorine analysis system.
  • FIG. 2 shows a block diagram of another exemplary total organic fluorine analysis system.
  • FIG. 3 is a flowchart showing an exemplary method for operating an exemplary total organic fluorine analysis system.
  • FIG. 4A shows a configuration of another exemplary total organic fluorine analysis system.
  • FIG. 4B shows another configuration of the system shown in FIG. 4A.
  • FIG. 4C shows another configuration of the system shown in FIG. 4A.
  • FIG. 5 A shows a temperature-PFOA mineralization diagram for exemplary systems and methods.
  • FIG. 5B shows an HRT-PFOA mineralization diagram for exemplary systems and methods.
  • FIG. 6A shows a time-response diagram for exemplary systems and methods.
  • FIG. 6B shows a fluoride-peak area diagram for exemplary systems and methods.
  • FIG. 6C shows a diagram depicting total fluorine analysis of an exemplary SCWO- TOF systems and methods, high-resolution mass spectrometry systems and methods, and total oxidizable precursor systems and methods.
  • FIG. 7 shows experimental results where the mass of fluoride evolved is reported as a function of the mass of organofluorine in DFE injected.
  • Systems, methods and techniques disclosed herein relate to analysis of organofluorine material.
  • Exemplary systems and methods leverage supercritical water oxidation (SCWO) and the unique properties of water above water’s critical point. Above water’s supercritical point and in the presence of abundant oxygen, organic contaminants, including organofluorine compounds such as poly- and per-fluoroalkyl substances (PFAS), are rapidly oxidized to inorganic species including carbon dioxide (CO2), fluoride ions (F‘), and water without the accumulation of potentially toxic intermediates.
  • SCWO supercritical water oxidation
  • PFAS poly- and per-fluoroalkyl substances
  • CO2 carbon dioxide
  • F‘ fluoride ions
  • Supercritical water provides advantages as a treatment medium for the destruction and oxidation of poly- and per-fluoroalkyl substances (PFAS), including rapid diffusion, effective solubilization of organic compounds, and complete mineralization of carbon dioxide (CO2) and inorganic salts.
  • PFAS poly- and per-fluoroalkyl substances
  • Systems, methods and techniques disclosed and contemplated herein may provide an automated benchtop organofluorine materials analysis system, capable of simultaneous measurement of free fluoride and total organic fluorine (TOF).
  • systems, methods and techniques disclosed and contemplated herein are based on a combination of one or more high- pressure fluid delivery pumps, a sample preparation unit, reactors, a pressure regulator unit, and an analysis unit.
  • the analysis unit is a high-sensitivity, in-line fluoride detection system.
  • Exemplary analysis units may be capable of analyzing samples in less than 10 minutes and may be capable of detecting less than 5 parts per billion (ppb) of organofluorine materials in aqueous samples.
  • Exemplary systems, methods and techniques disclosed and contemplated herein are capable of detecting organofluorine in small sample volumes (i.e., less than or equal to 250 pL for aqueous samples, or less than or equal to 1 mL for gas samples) without preconcentration, thereby avoiding potential loss of poorly adsorbed and/or eluted organofluorine materials.
  • Systems, methods and techniques disclosed and contemplated herein overcome bottlenecks and sensitivity loss associated with conventional combustion/ion chromatography (CIC) workflows.
  • Exemplary samples containing organofluorine materials may be mixed with low concentrations of oxidant and may be maintained in aqueous conditions before, during, and after complete oxidation to free fluoride (F‘) ions, thereby maintaining compatibility with online flow detection systems.
  • F‘ free fluoride
  • Optical sensing chemical probes may be utilized for the detection of free fluoride ions (F-).
  • Exemplary methods disclosed and contemplated may utilize changes in optical absorbance of an indicator compound.
  • An effluent containing free fluoride (F‘) ions from a supercritical water oxidation (SCWO) reactor may be mixed with a continuous flow of the indicator compound, which may be reacted together.
  • the chloride (CF) ions are displaced by fluoride (F‘) ions.
  • the reacted indicator compound with free fluoride (F‘) ions are provided to an analysis unit for quantification.
  • a dual -loop injection may be utilized to measure both background fluoride ions in aqueous samples and free fluoride (F‘) ions (i.e., oxidized total organic fluorine (TOF)).
  • F‘ free fluoride
  • An injection valve may be configured with two injection loops in series, which is provided from a single sample injection.
  • SCWO supercritical water oxidation
  • the sample in the second loop may be directed into a supercritical water oxidation (SCWO) reactor for conversion of organofluorine to free fluoride (F ) ions.
  • a timing valve may provide for completion of background fluoride measurement prior to detection of free fluoride (F’) ions (i.e., oxidized total organic fluorine (TOF)) from the supercritical water oxidation (SCWO) reactor. Subtractive analysis of any remaining residual inorganic fluoride present in samples may be used to account for background fluoride.
  • F free fluoride
  • SCWO supercritical water oxidation
  • the disclosed systems, methods and techniques provide high sensitivity for direct analysis of total poly- and per-fluoroalkyl substances (PFAS) in water, compared to currently available and/or previously disclosed systems and methods.
  • PFAS total poly- and per-fluoroalkyl substances
  • Exemplary systems and methods owing to the flowthrough configuration, may be integrated with a treatment process, thereby providing continuous performance monitoring, process control, and regulatory compliance.
  • the modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictate by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity).
  • the modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints.
  • the expression “from about 2 to about 4” also discloses the range “from 2 to 4.”
  • the term “about” may refer to plus or minus 10% of the indicated number.
  • “about 10% may indicate a range of 9% to 11%
  • “about 1” may mean from 0.9 - 1.1.
  • Other meanings of “about” may be apparent from the context, such as rounding off, so, for example “about 1” may also mean from 0.5 to 1.4.
  • each intervening number there between with the same degree of precision of numeric ranges herein is explicitly contemplated.
  • the numbers 7 and 8 are contemplated in addition to 6 and 9, and for the range of 6.0-7.0, the number 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are explicitly contemplated.
  • Exemplary systems and methods may utilize various materials for the analysis of organofluorine materials. Exemplary liquid streams, samples, and indicator compounds are discussed below.
  • Exemplary liquid streams disclosed and contemplated herein deliver samples to exemplary systems.
  • Exemplary liquid streams disclosed and contemplated herein comprise water.
  • exemplary liquid streams may also comprise one or more solvents.
  • exemplary liquid streams may also comprise one or more surfactants.
  • Exemplary liquid streams may comprise up to 70.0 weight percent (wt.%) organic matter.
  • exemplary liquid streams may comprise organic matter in an amount no greater than 70.0 wt.%; no greater than 60.0 wt.%; no greater than 50 wt.%; no greater than 40 wt.%; no greater than 30 wt.%; no greater than 20 wt.%; no greater than 10 wt.%; no greater than 5 wt.%; no greater than 1 wt.%; or no greater than 0.1 wt.%.
  • exemplary liquid streams may be primarily water.
  • exemplary liquid streams may comprise at least 99 weight percent (wt.%) water; at least 99.5 wt.% water; or at least 99.9 wt.% water.
  • Exemplary liquid streams are provided to exemplary systems and methods at high- pressure.
  • the high-pressure liquid stream may have a pressure between 20 MPa to 28 MPa, as discussed in greater detail below.
  • Exemplary samples are fluids.
  • exemplary samples may be liquid.
  • exemplary samples may be gaseous. Gaseous samples may comprise air, volatile compounds, semi-volatile compounds, gaseous organofluorine compounds, and combinations thereof.
  • exemplary samples may be liquid-solid slurries.
  • exemplary samples comprising organofluorine are not preconcentrated prior to being injected into a high-pressure liquid stream.
  • Exemplary samples may comprise dissolved organofluorine material.
  • Exemplary samples may comprise adsorbed organic fluorine, such as pulverized sorbents (e.g., spent activated carbon or ion exchange resins).
  • Exemplary organofluorine material may comprise fluoroalkyl material and/or fluorinated aromatic material.
  • organofluorine material comprises fluoroalkyl material.
  • exemplary fluoroalkyl material may comprise poly- and per-fluoroalkyl substances (PFAS), perfluorocarboxylic acids (PFCAs), perflurobutannoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoin acid (PFUnA), perfluorododecanoic acid (PFDoA), perfluorotridecanoic acid (PFTriA), perfluorotetradecanoic acid (PFTeDA), perfluorohexadecanoic acid (PFHxDA), perfluorobutane sulfonate
  • PFAS poly
  • Organofluorine material may comprise poly- and per-fluoroalkyl substances (PFAS).
  • PFAS poly- and per-fluoroalkyl substances
  • PFAS poly- and per-fluoroalkyl substances
  • PFAS poly- and per-fluoroalkyl substances
  • Challenges to the destruction of poly- and per-fluoroalkyl substances (PFAS) include effective and complete destruction of all organofluorine material, formation of lower molecular weight and/or volatile poly- and per-fluoroalkyl substances (PFAS) species during treatment, low-energy efficiency, particularly when other organic materials are present, and difficulty to account for all removed organic fluoride upon treatment.
  • Exemplary samples have a pH between 0 to 14; 1 to 14; 1 to 13; 2 to 13; 2 to 12; 3 to 12; 4 to 12; 4 to 11; 5 to 11; 5 to 10; 5 to 9; 6 to 9; 6 to 8; or about 7.
  • exemplary samples may have a pH of no less than 1; no less than 2; no less than 3; no less than 4; no less than 5; no less than 6; no less than 7; no less than 8; no less than 9; no less than 10; no less than 11; no less than 12; or no less than 13.
  • exemplary samples may have a pH of no greater than 14; no greater than 13; no greater than 12; no greater than 11; no greater than 10; no greater than 9; no greater than 8; no greater than 7; no greater than 6; no greater than 5; no greater than 4; no greater than 3; no greater than 2; or no greater than 1.
  • Exemplary aqueous samples may comprise an amount of organofluorine material of up to about 1000 parts per million (ppm).
  • exemplary samples may comprise an amount of organofluorine material of less than 1000 ppm; less than 100 ppm; less than 10 ppm; less than 1000 parts per billion (ppb); less than 750 ppb; less than 500 ppb; less than 250 ppb; less than 100 ppb; less than 50 ppb; less than 10 ppb; of less than 5 ppb; less than 4 ppb; less than 3 ppb; less than 2 ppb; less than 1 ppb; less than 0.1 parts per billion (ppb).
  • Exemplary gaseous samples may comprise an amount of organofluorine material of up to about 1000 parts per million by volume (ppmv).
  • exemplary samples may comprise an amount of organofluorine material of less than 1000 ppmv; less than 100 ppmv; less than 10 ppmv; less than 1000 parts per billion by volume (ppbv); less than 750 ppbv; less than 500 ppbv; less than 250 ppbv; less than 100 ppbv; less than 50 ppbv; less than 10 ppbv; of less than 5 ppbv; less than 4 ppbv; less than 3 ppbv; less than 2 ppbv; less than 1 ppbv; less than 0.1 parts per billion (ppbv).
  • Exemplary samples may be mixed with oxidant material.
  • oxidant material Various oxidant materials may be used.
  • exemplary oxidants may comprise hydrogen peroxide (H2O2), oxygen (O2), a potassium salt of persulfate, a sodium salt of persulfate, or combinations thereof.
  • Oxidant may be present in exemplary samples at various amounts.
  • An amount of oxidant used may be determined based on, for instance, an amount of organofluorine material.
  • an amount of oxidant used may be determined based on an amount of organic material, rather than an amount of organofluorine material.
  • oxidant material may be present in an amount that is between a 10 fold molar excess of oxidant material to organofluorine or organic material and a 100 fold molar excess of oxidant material.
  • oxidant material may be present in an amount that is no less than a 10 fold excess; no less than a 25 fold excess; no less than a 50 fold excess; no less than a 75 fold excess; or no less than a 100 fold excess amount relative to organofluorine material. In various implementations, oxidant material may be present in an amount that is no greater than a 100 fold excess; no greater than a 75 fold excess; no greater than a 50 fold excess; no greater than a 25 fold excess; or no greater than a 10 fold excess relative to organofluorine or organic material.
  • exemplary indicator compounds exhibit a change in optical properties after a chemical reaction involving fluorine.
  • exemplary indicator compounds may comprise a dye.
  • exemplary indicator compounds may be provided in solution.
  • exemplary indicator compounds react with a fluorine-containing species, where a chloride (O’) ion of the indicator compound is replaced by a fluoride (F‘) ion from the fluorine-containing species.
  • optical absorbance of exemplary indicator compounds decreases at 610 nm after displacement of chloride (O') ions by fluoride (F‘) ions. In some instances, optical absorbance of exemplary indicator compounds increases at 637 nm after displacement of the chloride (C1‘) ions by fluoride (F‘) ions from the fluorine-containing species.
  • FIG. 1 shows an exemplary total organic fluorine analysis system 100.
  • exemplary total organic fluorine analysis system 100 includes liquid source 102, indicator source 104, sample preparation unit 106, reactor 108, cooling unit 110, pressure regulator unit 112, mixing unit 114, reactor 116, analysis unit 118, background sample 120, and sample source 122.
  • Other embodiments may include more of fewer components.
  • Exemplary total organic fluorine analysis system 100 may be capable of detecting organofluorine material in an aqueous sample at an amount of 1000 parts per billion or less. [0056] Total organic fluorine analysis system 100 may be capable of analyzing samples comprising organofluorine material in a time period suitable for continuous performance monitoring, process control, and/or regulatory compliance. For instance, total organic fluorine analysis system 100 may complete an analysis of an exemplary sample comprising organofluorine materials in a time period of no more than 10 minutes per sample.
  • Liquid source 102 is configured to provide a high-pressure liquid stream. Typically, liquid source 102 is in fluid communication with sample preparation unit 106.
  • Sample preparation unit 106 may combine an exemplary sample with a high-pressure liquid stream. Sample preparation unit 106 may be configured to provide a sample in plug flow to downstream units. In some instances, Sample preparation unit 106 may be configured to provide a sample in continuous flow to downstream units.
  • Sample preparation unit 106 may be configured to provide a background sample 120 to mixing unit 114.
  • Sample preparation unit 106 is in fluid communication with reactor 108.
  • Sample preparation unit 106 is in fluid communication with exemplary mixing unit 114.
  • Sample preparation unit 106 may be automatic or manually operated to provide a sample to an input stream, generally by maintaining plug flow in the input stream.
  • exemplary sample preparation unit 106 may be an autosampler.
  • Sample preparation unit 106 may also bring a sample to a required system pressure (the supercritical pressure).
  • Reactor 108 is configured to heat a reactor input to water’s supercritical temperature and supercritical pressure. Reactor 108 is in fluid communication with, and provides an output stream to, cooling unit 110.
  • Reactor 108 may have various lengths and volumes which, in combination with various flow rates, provide desired residence times.
  • reactor 108 may have a volume that is at least 1.5 times a volume of an injected sample at the conditions of the reaction (supercritical conditions).
  • reactor 108 may have a length between 1 meter and 5 meters.
  • reactor 108 may have an inner diameter between 1.0 mm and 1.4 mm.
  • exemplary reactor 108 may be a supercritical water oxidation reactor.
  • exemplary reactor 108 may be positioned within a tube furnace. A flow path through exemplary reactor 108 may be coiled.
  • reactor 108 is constructed of a material that is heat and oxidation resistant.
  • reactor 108 may be constructed of an Inconel alloy, such as Inconel 625, or a Hastelloy alloy, such as Hastelloy C.
  • Cooling unit 110 is configured to decrease the temperature of the output stream of exemplary reactor 108. Cooling unit 110 may decrease the temperature of the output stream from reactor 108 to subcritical temperatures. Cooling unit 110 provides an output stream to, and is in fluid communication with, pressure regulator unit 112.
  • Pressure regulator unit 112 may be configured to maintain a constant pressure of components upstream from pressure regulator unit 112. Pressure regulator unit 112 may decrease the pressure of the output stream from exemplary cooling unit 110 to subcritical pressures. Pressure regulator unit 112 provides an output stream to, and is in fluid communication with, exemplary mixing unit 114.
  • Mixing unit 114 receives the decompressed cooled output stream from pressure regulator unit 112. Mixing unit 114 also receives an exemplary indicator compound from indicator source 104. Mixing unit 114 mixes together the decompressed cooled output and the continuous flow of the exemplary indicator compound. Mixing unit 114 provides an output stream to, and is in fluid communication with, reactor 116.
  • Mixing unit 114 may be a static mixer. Mixing unit 114 may have various sizes relative to potential reactor 108 flow rates and indicator source 104 flow rates. For instance, mixing unit 114 may have a volume between 25 pL and 200 pL for a total input flow rate of about 0.5 mL/minute. Mixing unit 114 may be sized differently for other implementations.
  • Indicator source 104 provides indicator compound to, and is in fluid communication with, mixing unit 114. In some instances, indicator source 104 provides a continuous stream of indicator compound to mixing unit 114. In some instances, a control unit (not shown) may selectively provide indicator compound from indicator source 104 to mixing unit 114.
  • Reactor 116 may be configured to operate at a temperature between 25 °C to 65 °C. In various embodiments, heat is transferred by exemplary reactor 116 to an indicator mixture causing a reaction between the exemplary indicator compound and the fluoride ions (F ) compounds. During exemplary reactions, chloride ions (CF) of the indicator compound are displaced and the fluoride ions (F‘) replace the chloride ions in the indicator compound.
  • Reactor 116 provides an output stream to, and is in fluid communication with, analysis unit 118.
  • Analysis unit 118 may be configured to determine an amount of reacted organofluorine material in the exemplary sample. Analysis unit 118 may be configured to measure absorbance and/or fluorescence.
  • Analysis unit 118 may comprise various components to analyze an output stream from reactor 116. Exemplary components include, but are not limited to, a controller, a light emitter, a light detector, and a data storage device. In some instances, analysis unit 118 may comprise a fluorescence probe and/or an absorbance probe.
  • Exemplary controllers may comprise a processor and a data storage device, which may communicate over one or more connections or buses.
  • An exemplary processor may be one or more of a microprocessor, application-specific integrated circuit (ASIC), or another suitable electronic device.
  • ASIC application-specific integrated circuit
  • the data storage device may be a memory device, which may include read-only memory (ROM), random access memory (RAM) (for example, dynamic RAM (DRAM), synchronous DRAM (SDRAM), and the like), electrically erasable programmable read-only memory (EEPROM), flash memory, a hard disk, a secure digital (SD) card, other suitable memory devices, or a combination thereof.
  • the electronic processor executes computer-readable instructions (“software”) stored in the memory.
  • the software may include firmware, one or more applications, program data, filters, rules, one or more program modules, and other executable instructions.
  • the software may include instructions and associated data for performing the methods described herein. It should be understood that the functionality described herein as being performed by the analysis unit 118 may be distributed among multiple software modules, hardware components, or a combination thereof stored or included in a computing device associated with analysis unit 118.
  • Analysis unit 118 directs light into an output stream from reactor 116. As mentioned above, some samples may be background fluorine samples provided directly from sample preparation unit 106 to mixing unit 114. [0077] Analysis unit 118 measures the light absorbed, transmitted, or emitted by the sample of the output stream from exemplary reactor 116 at each wavelength. For instance, analysis unit 118 may generate and analyze a UV absorbance spectrum. Analysis unit 118 determines an absorbance peak based on, at least, the generated UV absorbance spectrum.
  • Analysis unit 118 calculates a threshold percentage of organofluorine material, where the area under the determined absorbance peak is the amount of reacted organofluorine material (i.e., the amount of fluoride ions displaced the chloride ion of the exemplary indicator compounds).
  • the light transmitted from analysis unit 118 includes light from the ultraviolet (UV) to visible light wavelength spectrum, e.g., 190 nm to 900 nm.
  • UV ultraviolet
  • the analysis unit 118 calculates a threshold difference between the amount of reacted organofluorine material and the amount of organofluorine material present in the background sample 120. Using the determined difference, the analysis unit 118 may determine how much of the initial organofluorine material was oxidized in the exemplary total organic fluorine analysis system 100.
  • FIG. 2 shows an exemplary total organic fluorine system 200 combined with a stop flow.
  • total organic fluorine system 200 combined with a stop flow includes similar components as total organic fluorine system 100, as described above.
  • the system 200 includes liquid source 102, indicator source 104, sample preparation unit 106, reactor 108, cooling unit 110, pressure regulator unit 112, mixing unit 114, reactor 116, analysis unit 118, background sample 120, and sample source 122.
  • total organic fluorine system 200 combined with a stop flow also includes stop flow 202 and valve 204.
  • total organic fluorine system combined with a stop flow 200 may be configured to redirect the flow of the first reactor input around exemplary reactor 108.
  • Other embodiments may include more of fewer components.
  • the redirected flow of the first reactor input may comprise unreacted organofluorine material and partially or fully oxidized fluoride (F‘) ion compounds.
  • F‘ oxidized fluoride
  • Exemplary methods of analyzing a sample comprising organofluorine material may comprise various operations.
  • FIG. 3 shows example method 300 for analyzing a sample comprising organofluorine material.
  • method 300 includes providing a first reactor input to a first reactor (operation 302), heating a first reactor input to supercritical temperature and pressure (operation 304), cooling an output of the first reactor (operation 306), adjusting a pressure of the cooled first reactor output (operation 308), mixing the decompressed cooled first reactor output with an indicator compound (operation 310), providing an indicator mixture to a second reactor (operation 312), heating a second reactor input (operation 314), providing a second reactor output to an analysis unit (operation 316), and determining an amount of organofluorine material present in the sample (operation 318).
  • Other embodiments may include more or fewer operations. Exemplary systems described and contemplated herein can be utilized to perform the operations of method 300.
  • the operations included in method 300 may allow for continuous performance monitoring, process control, and/or regulatory compliance.
  • the operations included in method 300 may be completed in a time period suitable for controls and/or compliance.
  • operations included in method 300 may complete an analysis of an exemplary sample comprising organofluorine materials in a time period of no more than 10 minutes per sample.
  • Method 300 may begin by injecting an exemplary sample into a high-pressure liquid stream and providing a first reactor input to a first reactor (operation 302). Samples may be injected as plugs into a high-pressure liquid stream.
  • Exemplary injected liquid samples may comprise a volume of no more than 250 pL.
  • exemplary liquid samples may comprise a volume of no more than 250 pL; no more than 225 pL; no more than 200 pL; no more than 175 pL; no more than 150 pL; no more than 125 pL; no more than 100 pL; no more than 75 pL; no more than 50 pL; no more than 25 pL; no more than 15 pL; no more than 10 pL; no more than 5 pL; and no more than 1 pL.
  • exemplary liquid samples may comprise a volume between 0.001 pL to 250 pL; 0.001 pL to 225 pL; 0.001 pL to 200 pL; 0.001 pL to 175 pL; 0.001 pL to 150 pL; 0.001 pL to 125 pL; 0.001 to 100 pL; 0.001 pL to 50 pL; 0.001 pL to 25 pL; 0.001 pL to 10 pL; 0.001 pL to 5 pL; 0.001 pL to 1 pL; 0.001 pL to 0.5 pL; 0.001 pL to 0.1 pL; 0.001 pL to 0.05 pL; or 0.001 to 0.01 pL.
  • exemplary liquid samples may comprise a volume of no greater than 250 pL; no greater than 225 pL; no greater than 175 pL; no greater than 125 pL; no greater than 75 pL; no greater than 50 pL; no greater than 25 pL; no greater than 15 pL; no greater than 10 pL; no greater than 1 pL; no greater than 0.1 pL; or no greater than 0.01 pL.
  • exemplary liquid samples may comprise a volume of no less than 0.001 pL; no less than 0.005 pL; no less than 0.01 pL; no less than 0.05 pL; no less than 0.1 pL; no less than 0.5 pL; no less than 1 pL; no less than 5 pL; no less than 15 pL; no less than 35 pL; no less than 50 pL; no less than 100 pL; no less than 150 pL; or no less than 200 pL.
  • Exemplary injected gas/air samples may comprise a volume of no more than 1 L.
  • gas/air samples may be subjected to cryogenic concentration, and in those instances, larger volumes may be used, such as 10L or more.
  • cryogenic sample concentration involves passing a gaseous sample in a cooled loop, such as a liquid nitrogen cooled loop, which condenses volatile compounds. Subsequently, the loop may be reheated to release volatile compounds into the analytical system.
  • exemplary gas samples may comprise a volume of no more than IL; no more than 500 mL; no more than 250 mL; no more than 200 mL; no more than 100 mL; no more than 75 mL; no more than 50 mL; no more than 25 mL; no more than 10 mL; or no more than 1 mL.
  • exemplary gas samples may comprise a volume of no less than 1 mL; no less than 15 mL; no less than 30 mL; no less than 60 mL; no less than 100 mL; no less than 150 mL; no less than 400 mL; no less than 500 mL; no less than 750 mL; or no less than 1 L.
  • the high-pressure liquid stream may have a pressure between 20 MPa to 28 MPa.
  • the high-pressure liquid stream may have a pressure between 20 MPa to 28 MPa; 20 to 27 MPa; 20 to 26 MPa; 20 to 25 MPa; 21 to 27 MPa; 21 to 26 MPa; 21 to 25 MPa; 21 MPa to 24 MPa; 22 MPa to 24 MPa; 22 MPa to 28 MPa; 22 MPa to 27 MPa; 22 MPa to 26 MPa; 23 MPa to 28 MPa; 23 MPa to 27 MPa; 23 MPa to 26 MPa; 24 MPa to 28 MPa; 24 MPa to 27 MPa; 24 MPa to 26 MPa; or about 26 MPa.
  • the high-pressure liquid stream may have a pressure of no less than 20 MPa; no less than 21 MPa; no less than 22 MPa; no less than 22 MPa; no less than 23 MPa; no less than 24 MPa; no less than 25 MPa; no less than 26 MPa; or no less than 27 MPa.
  • the high-pressure liquid stream may have a pressure of no greater than 28 MPa, no greater than 27.5 MPa; no greater than 26.5 MPa; no greater than 25.5 MPa; no greater than 24.5 MPa; no greater than 23.5 MPa; no greater than 22.5 MPa; no greater than 21.5 MPa; or no greater than 20.5 MPa.
  • Exemplary methods may provide an input to a first reactor at various flow rates.
  • the first reactor input may have a flow rate between 0.1 mL/min to 2.0 mL/min. In various implementations, the first reactor input may have a flow rate between 0.
  • the first reactor input may have a flow rate of no less than 0.1 mL/min; no less than 0.3 mL/min; no less than 0.5 mL/min; no less than 0.7 mL/min; no less than 0.9 mL/min; no less than 1.1 mL/min; no less than 1.3 mL/min; no less than 1.5 mL/min; no less than 1.7 mL/min; or no less than 1.9 mL/min.
  • the first reactor input may have a flow rate of no greater than 2.0 mL/min; no greater than 1.8 mL/min; no greater than 1.6 mL/min; no greater than 1.4 mL/min; no greater than 1.2 mL/min; no greater than 1.0 mL/min; no greater than 0.8 mL/min; no greater than 0.6 mL/min; no greater than 0.4 mL/min; or no greater than 0.2 mL/min.
  • the first reactor input is heated to supercritical temperature and pressure (operation 304).
  • the first reactor operates to oxidize the organofluorine material into one or more fluoride compounds (i.e., F ).
  • the first reactor may be operated at a temperature between 400 °C and 660 °C. In various implementations, the first reactor may be operated at a temperature between 400 °C and 660 °C; 400 °C to 650 °C; 425 °C; to 650 °C; 450 °C to 650 °C; 450 °C; to 625 °C; 475 °C; to 600 °C; 475 °C; to 575 °C; 475 to 550 °C; 475 °C to 525 °C; or about 500 °C.
  • the first reactor may be operated at a temperature no less than 400 °C; no less than 450 °C; no less than 500 °C; no less than 550 °C; no less than 600 °C; or no less than 650 °C. In various implementations, the first reactor may be operated at a temperature of no greater than 660 °C; no greater than 650 °C; no greater than 625 °C; no greater than 575 °C; no greater than 525 °C; no greater than 475 °C; or no greater than 425 °C.
  • the flow rate and the length of the reactor may be configured such that a residence time in the first reactor may be from 5 seconds to 300 seconds (operation 304).
  • a residence time in the first reactor may be from 5 seconds to 300 seconds; 5 seconds to 280 seconds; 5 seconds to 240 seconds; 10 seconds to 240 seconds; 15 seconds to 240 seconds; 30 seconds to 240 seconds; 30 seconds to 220 seconds; 30 seconds to 200 seconds; 30 seconds to 180 seconds; 60 seconds to 180 seconds; or about 120 seconds.
  • a residence time in the first reactor may be no less than 5 seconds; no less than 20 seconds; no less than 40 seconds; no less than 60 seconds; no less than 80 seconds; no less than 100 seconds; no less than 120 seconds; no less than 160 seconds; no less than 200 seconds; no less than 220 seconds; no less than 240 seconds; or no less than 280 seconds.
  • a residence time in the first reactor may be no greater than 300 seconds; no greater than 270 seconds; no greater than 250 seconds; no greater than 230 seconds; no greater than 210 seconds; no greater than 170 seconds; no greater than 150 seconds; no greater than 130 seconds; no greater than 110 seconds; no greater than 70 seconds; no greater than 30 seconds; or no greater than 10 seconds.
  • an output stream from the first reactor is cooled (operation 306).
  • a cooling unit cools the output stream from the first reactor to a subcritical temperature and subcritical pressure.
  • a cooling unit may decrease a temperature of the output stream from the first reactor to a temperature between 4 °C to 25 °C.
  • a cooling unit may decrease the temperature of the output stream from the first reactor to a temperature between 4 to 25 °C; 4 °C to 23 °C; 4 °C to 21 °C; 5 °C to 21 °C; 5 °C to 20 °C; 5 °C to 18 °C; 6 °C to 18 °C; 8 °C to 18 °C; 8 °C to 16 °C; 10 °C to 16 °C; 12 °C to 16 °C; or about 15 °C.
  • a cooling unit may decrease the temperature of the output stream from the first reactor to a temperature of no less than 4 °C; no less than 6 °C; no less than 8 °C; no less than 10 °C; no less than 12 °C; no less than 14 °C; no less than 16 °C; no less than 18 °C; no less than 20 °C; no less than 22 °C; or no less than 24 °C.
  • a cooling unit may decrease the temperature of the output stream from the first reactor to a temperature of no greater than 25 °C; no greater than 23 °C; no greater than 21 °C; no greater than 19 °C; no greater than 17 °C; no greater than 15 °C; no greater than 13 °C; no greater than 11 °C; no greater than 9 °C; no greater than 7 °C; or no greater than 5 °C.
  • the cooled first reactor output stream pressure is adjusted (operation 308).
  • a pressure regulator unit may decrease the pressure of the cooled first reactor output to a subcritical pressure during operation 308.
  • the pressure regulator unit may decrease the pressure of the cooled first reactor output stream to a pressure between 0.1 MPa to 0.6MPa.
  • the pressure regulator unit may decrease the pressure of the cooled first reactor output stream to a pressure between 0. IMPa to 0.6MPa; 0. IMPa to 0.5MPa to 0. IMPa to 0.4MPa; O.
  • the pressure regulator unit may decrease the pressure of the cooled first reactor output stream to a pressure no less than 0. IMPa; no less than 0.3MPa; or no less than 0.5MPa. In various implementations, the pressure regulator unit may decrease the pressure of the cooled first reactor output stream to a pressure no greater than 0.6MPa; no greater than 0.4MPa; or no greater than 0.2MPa.
  • the decompressed cooled first reactor output stream may be mixed with an indicator compound (operation 310), thereby generating an indicator mixture.
  • a mixing unit receives a decompressed cooled first reactor output stream from the pressure regulator unit and receives a flow of an exemplary indicator compound from an indicator source. Exemplary indicator compounds are discussed in greater detail above.
  • Exemplary indicator compounds may be provided to the mixing unit at various flowrates, which may relate to a concentration of indicator compound in the stream.
  • exemplary indicator compounds may be provided to the mixing unit at a flowrate of 50 to 500 pL/min; 20 to 400 pL/min; 30 to 300 pL/min; 40 to 200 pL/min; 50 to 100 pL/min; 100 to 400 pL/min; or 75 to 25300 pL/min.
  • Exemplary indicator compounds may be provided to the mixing unit at a flowrate of no less than 50 pL/min; no less than 60 pL/min; no less than 70 pL/min; no less than 80 pL/min; no less than 90 pL/min; no less than 100 pL/min; no less than 200 pL/min; no less than 300 pL/min; no less than 400 pL/min; or no less than 500 pL/min.
  • Exemplary indicator compounds may be provided to the mixing unit at a flowrate of no greater than 500 pL/min; no greater than 400 pL/min; no greater than 300 pL/min; no greater than 200 pL/min; no greater than 150 pL/min; no greater than 100 pL/min; no greater than 95 pL/min; no greater than 85 pL/min; no greater than 75 pL/min; no greater than 65 pL/min; or no greater than 55 pL/min.
  • an indicator mixture may be provided to a second reactor (operation 312).
  • the output stream from the mixing unit to the second reactor may have a flowrate between 0.1 mL/min to 2.0 mL/min. In various implementations, the output stream from the mixing unit to the second reactor may have a flowrate between 0.1 mL/min to 2.0 mL/min; 0.1 mL/min to 1.8 mL/min; 0.1 to 1.6 mL/min; 0.1 mL/min to 1.5 mL/min; 0.2 mL/min to 1.5 mL/min; 0.3 mL/min to 1.5 mL/min; 0.5 mL/min to 1.5 mL/min; 0.5 mL/min to 1.3 mL/min; 0.6 mL/min to 1.3 mL/min; 0.8 mL/min to 1.3 mL/min; 0.8 mL/min to 1.1 mL/min; or about 1 mL/min.
  • the output stream from the mixing unit to the second reactor may have a flowrate of no less than 0.1 mL/min; no less than 0.3 mL/min; 0.5 mL/min; 0.7 mL/min; 0.9 mL/min; 1.1 mL/min; 1.3 mL/min; 1.5 mL/min; 1.7 mL/min; or 1.9 mL/min.
  • the output stream from the mixing unit to the second reactor may have a flowrate of no greater than 2.0 mL/min; 1.8 mL/min; 1.6 mL/min; 1.4 mL/min; 1.2 mL/min; 1.0 mL/min; 0.8 mL/min; 0.6 mL/min; 0.4 mL/min; 0.2 mL/min.
  • the second reactor input is heated in a second reactor (operation 314).
  • the second reactor may be heated to a temperature between 25 °C and 65 °C.
  • the second reactor may be heated to a temperature between 25 °C and 65 °C; 25 °C to 60 °C; 25 °C to 55 °C; 30 °C to 65 °C; 35 °C to 65 °C; 35 °C to 60 °C; 40 °C to 60 °C; 45 °C to 60 °C; 45 °C to 55 °C; or 50 °C to 55 °C.
  • the second reactor may be heated to a temperature of no less than 25 °C; no less than 30 °C; no less than 40 °C; no less than 50 °C; or no less than 60 °C. In various implementations, the second reactor may be heated to a temperature of no greater than 65 °C; no greater than 55 °C; no greater than 45 °C; no greater than 35 °C; or no greater than 30 °C.
  • the flow rate and the length of the reactor may be configured such that a residence time in the first reactor may be from 5 seconds to 240 seconds.
  • the second reactor may have a residence time of 5 seconds to 240 seconds; 10 seconds to 240 seconds; 15 seconds to 240 seconds; 30 seconds to 240 seconds; 30 seconds to 220 seconds; 30 seconds to 200 seconds; 30 seconds to 180 seconds; 60 seconds to 180 seconds; or about 120 seconds.
  • the second reactor may have a residence time of no less than 5 seconds; no less than 20 seconds; no less than 40 seconds; no less than 60 seconds; no less than 80 seconds; no less than 100 seconds; no less than 120 seconds; no less than 160 seconds; no less than 200 seconds; or no less than 220 seconds.
  • the second reactor may have a residence time of no greater than 240 seconds; no greater than 230 seconds; no greater than 210 seconds; no greater than 170 seconds; no greater than 150 seconds; no greater than 130 seconds; no greater than 110 seconds; no greater than 70 seconds; no greater than 30 seconds; or no greater than 10 seconds.
  • an analysis unit may use a light source to illuminate a second reactor output with light.
  • the illuminated light may be in the ultraviolet visible (UV) spectrum to the visible wavelength spectrum.
  • the analysis unit measures the light absorbed, transmitted, or emitted by the sample of the second reactor output at each wavelength across the spectrum described above. That is, the analysis unit may be configured to measure absorbance and/or fluorescence.
  • the analysis unit may generate a UV absorbance spectrum.
  • the analysis unit determines an absorbance peak based on, at least, the generated UV absorbance spectrum.
  • the analysis unit calculates a threshold percentage of organofluorine material, where the area under the determined absorbance peak is the amount of reacted organofluorine material (i.e., the amount of fluoride ions displaced the chloride ion of the exemplary indicator compounds).
  • an amount of background fluorine present in the sample may be determined prior to determining an amount of organofluorine material present in the sample. That is, operation 318 may include calculating a threshold difference between an amount of reacted organofluorine material and an amount of organofluorine material present in a background sample. Using the determined difference, it may be determined how much of the initial organofluorine material was oxidized in the exemplary total organic fluorine analysis system.
  • System 500 includes sample injection source 502, valving unit 504, high pressure pump 506, valving unit 508, optical fluoride (F-) detection system 510, supercritical water oxidation (SCWO) reactor 511, and conduits 512, 514, 516, 517, 518, 520, and 522.
  • An initial operation may include injecting an aqueous sample from source 502 into unit 504.
  • Unit 504 includes configurable inputs and outputs, labeled 1-10. The injected sample may enter a reactor loop 512 and a bypass loop 514.
  • High pressure pump 506 maintains pressurization of SCWO reactor 511.
  • the connections in valving unit 504 may be adjusted in a subsequent operation.
  • high pressure pump 506 loads the reactor loop into SCWO reactor 511 under supercritical conditions.
  • the bypass loop is isolated.
  • the connections in valving unit 508 may be adjusted in a subsequent operation.
  • the SCWO reactor 511 is isolated at high temperature and pressure for a static reaction.
  • High pressure pump 506 transfers the bypass loop to optical fluoride detection system 510 for analysis.
  • connections in valving unit 504 and valving unit 508 may be adjusted to the configuration shown in FIG. 4A.
  • high pressure pump 506 may transfer reaction products from the SCWO reactor 511 to optical fluoride detection system 510 for analysis.
  • a high- pressure piston pump was used to deliver a water flow at 200 pL/min to a high-pressure injection valve, which allowed for injection of a 200 pL plug of organofluorine-containing aqueous sample (premixed with 50 pM H2O2) into a continuous flow stream at 3,800 psi pressure.
  • This sample plug and associated flowing stream was directed into a reactor consisting of 4 meters of coiled 0.0625” OD (1.59 mm) x 0.040” ID (1.02 mm) Hastelloy C tubing held at 600° C in a quartz-lined tube furnace.
  • the now supercritical flow stream was cooled by a water- jacketed heat exchanger and decompressed with a spring-loaded backpressure regulator prior to being directed to a 25 pL mixing tee.
  • the cooled and decompressed reactor effluent was combined with a 100 pL/min continuous flow of ethanol containing 200 pM of aluminum (III) phthalocyanine chloride.
  • the resulting mixture was directed to a 0.0625” OD stainless steel reactor coil with total volume 1.0 mL, held at a continuous temperature of 55° C.
  • the solution was directed to a diode-array UV-VIS absorbance detector fitted with a flow cell, and absorbance measurements at 637 nm and 610 nm were continuously recorded. Fluoride quantitation was performed by differential absorbance measurements at these two wavelengths, calibrated against solutions of known fluoride concentration.
  • FIG. 5 A shows a temperature-PFOA mineralization diagram for exemplary systems and methods.
  • FIG. 5A further shows the optimization of the effect of temperature against a constant reaction time of 37 seconds for exemplary systems and methods, illustrating approximately 100% conversion of PFOA to fluoride under optimized conditions.
  • FIG. 5B shows an HRT-PFOA mineralization diagram for exemplary systems and methods.
  • FIG. 5B further shows the optimization of the effect of reaction time (HRT) against a constant temperature at 600 °C, wherein PFOA mineralization to fluoride was complete in less than 40 seconds of reaction time.
  • HRT reaction time
  • FIGS. 5A and 5B show the optimization of exemplary systems and methods for mineralization of a sample of perfluorooctanoic acid (PFOA) at 1 part per million (ppm) and uses 50 pM hydrogen peroxide as an oxidant source in neutral (unbuffered) water.
  • PFOA perfluorooctanoic acid
  • FIG. 6A shows a time-response diagram for exemplary systems and methods for the analysis of an aqueous sample.
  • FIG. 6A further shows the sensitivity of exemplary systems and methods, demonstrating response at concentrations between 5 - 1000 parts per billion (ppb) organofluorine-derived fluoride.
  • FIG. 6B shows a fluoride-peak area quantitative response graph for exemplary systems and methods.
  • FIG. 6B further shows a linear response of exemplary systems and methods with a differential absorbance AlPc-Cl optical sensor detection method for fluoride analysis.
  • FIGS 6A and 6B it was determined that exemplary systems and methods provided a sensitive detection and were capable of detecting fluoride at less than 5 parts per billion (ppb) in aqueous samples within 10 minutes.
  • FIG. 6C shows a diagram depicting total fluorine quantitation results for aqueous samples using an exemplary SCWO-TOF systems and methods, high-resolution mass spectrometry systems and methods, and total oxidizable precursor systems and methods.
  • AFFF undiluted aqueous fdm-forming foam
  • Air samples with different concentrations of 1 , 1 -difluoroethane were prepared by diluting DFE with ambient air. DFE was used as model volatile or gaseous PFAS compound.
  • small samples (50 pL) of air containing DFE were injected in a 1 mL sample loop (“reactor loop” 512 on Figure 4C) as follows.
  • the sample loop was first loaded with about 0.5 mL of either water or 0.05% hydrogen peroxide (H2O2). Then 50 pL of air containing DFE was loaded, and then another volume of about 0.5 mL of either water or 0.05% hydrogen peroxide was loaded into the sample loop, thus forming a small slug of air flanked by either water or hydrogen peroxide.
  • hydrogen peroxide was used, it served as the oxidant, but other oxidants can be used.
  • oxygen in the air sample served as the oxidant.
  • Results are shown in FIG. 7, in which the mass of fluoride evolved is reported as a function of the mass of organofluorine in DFE injected.
  • Two different sets of experiments are reported, one where the air sample containing DFE was injected together with hydrogen peroxide as oxidant, and one where the air sample containing DFE was flanked by water. No significant differences could be observed indicating that the oxygen in the air samples and/or the conditions in the SCWO reactor were sufficient to defluorinate the injected DFE.
  • FIG. 7 also illustrates that there was a linear behavior between the fluoride recovered and the organofluorine injected. In this case, the recovery (or mineralization) was on average 70%. No attempts were made to either optimize the recovery or elucidate why it was not 100%.
  • a method of analyzing a sample comprising organofluorine material comprising: providing a first reactor input to a first reactor with a high-pressure liquid stream, the first reactor input comprising the sample; in the first reactor, heating the first reactor input to a supercritical temperature and pressure; cooling an output stream from the first reactor to a subcritical temperature; adjusting a pressure of the cooled first reactor output stream to a subcritical pressure; mixing the decompressed cooled first reactor output stream with an indicator compound to generate an indicator mixture; providing the indicator mixture to a second reactor; heating the indicator mixture in the second reactor, thereby causing a reaction of the indicator compound with a fluorine-containing species and generating a second reactor output; providing the second reactor output to an analysis unit; and with the analysis unit, determining an amount of organofluorine material present in the sample.
  • Clause 4 The method according to any one of clauses 1-3, wherein the sample is liquid; and wherein the amount of organofluorine material present in the sample is less than 1000 parts per million (ppm).
  • Clause 5. The method according to any one of clauses 1-3, wherein the sample is gaseous; and wherein the amount of organofluorine material present in the sample is less than 1000 parts per million by volume (ppmv).
  • Clause 6 The method according to any one of clauses 1-5, the first reactor input being provided such that a residence time in the first reactor is between 5 seconds and 300 seconds.
  • Clause 7 The method according to any one of clauses 1-6, the second reactor input being provided such that a residence time in the second reactor is between 5 seconds and 240 seconds.
  • Clause 8 The method according to any one of clauses 1-7, wherein the first reactor input has a flowrate between 0.1 mL/ min and 2.0 mL/min.
  • Clause 9 The method according to any one of clauses 1-8, wherein the second reactor input has a flowrate between 0.1 mL/min and 2.0 mL/min.
  • Clause 10 The method according to any one of clauses 1-9, wherein a temperature within the first reactor is between 400 °C and 660 °C.
  • Clause 13 The method according to any one of clauses 1-12, wherein when the sample is a liquid, a volume of the liquid sample is less than or equal to 250 pL; wherein when the sample is a gas, a volume of the gaseous sample is less than or equal to 1 L; and wherein the sample has not been preconcentrated.
  • Clause 14 The method according to any one of clauses 1-13, wherein a pressure of the high- pressure liquid stream is between 20 MPa and 28 MPa.
  • Clause 15 The method according to any one of clauses 1-14, wherein the subcritical temperature is between 4 °C and 25 °C; and wherein the subcritical pressure is between 0.1 MPa and 0.6 MPa.
  • Clause 16 The method according to any one of clauses 1-15, further comprising, with the analysis unit, determining an amount of reacted indicator compound in the second reactor output.
  • Clause 17 The method according to clause 16, further comprising measuring an optical absorbance shift in the second reactor output.
  • Clause 18 The method according to any one of clauses 1-17, further comprising: after providing the sample to the first reactor, actuating a valve assembly to close the first reactor inlet and outlet; and after a predetermined amount of time, opening the first reactor inlet and outlet.
  • Clause 19 The method according to any one of clauses 1-18, further comprising: providing a background sample to the analysis unit with the high-pressure liquid stream, the background sample comprising unreacted organofluorine material; and with the analysis unit, determining the amount of fluoride in the background sample.
  • Clause 20 The method according to clause 19, further comprising: determining an amount of reacted fluorine of the second reactor input based on, at least, the amount of fluoride in the background sample.
  • a system for analyzing a sample comprising: a sample preparation unit in fluid communication with a high-pressure liquid source and a sample source; a first reactor comprising a first reactor inlet and a first reactor outlet, the first reactor inlet being in fluid communication with the sample preparation unit, and the first reactor configured to heat a first reactor input to a supercritical temperature and pressure; a cooling unit in fluid communication with the first reactor output; a pressure regulator unit in fluid communication with an output stream from the cooling unit; a mixing unit in fluid communication with the pressure regulator unit and in fluid communication with an indicator compound source; a second reactor comprising a second reactor inlet and a second reactor outlet, the second reactor inlet being in fluid communication with the mixing unit, and the second reactor configured to heat a second reactor input to a reaction temperature; and an analysis unit in fluid communication with the second reactor outlet, configured to determine an amount of organofluorine material present in the sample.
  • Clause 24 The system according to any of clauses 21-23, wherein the sample is a liquid; wherein the amount of organofluorine material present in the sample is less than 5 parts per billion (ppb).
  • Clause 25 The system according to any of clauses 21-23, wherein the sample is a liquid; and wherein the amount of organofluorine present in the sample is less than 1 parts per billion (ppb).
  • Clause 27 The system according to any of clauses 21-26, the analysis unit comprising a UV/VIS detector.
  • Clause 28 The system according to any of clauses 21-27; and the analysis unit being configured to analyze an optical absorbance shift of an output stream from the second reactor.
  • Clause 29 The system according to any of clauses 21-28, further comprising: a valve assembly in fluid communication with the first reactor inlet and the first reactor outlet, wherein the valve assembly is actuated to close the first reactor inlet and first reactor outlet, and opening the first reactor inlet and first reactor outlet after a predetermined amount of time.
  • Clause 30 The system according to any of clauses 21-29, further comprising: the sample preparation unit in fluid communication with the analysis unit, wherein a background sample is provided to the analysis unit, the background sample comprising unreacted organofluorine material, and with the analysis unit, determining an amount of fluoride in the background sample.

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Abstract

Des systèmes et des procédés donnés à titre d'exemple concernent l'analyse d'un échantillon comprenant un matériau organofluoré. Des échantillons donnés à titre d'exemple comprennent des échantillons liquides et des échantillons gazeux, qui peuvent être fournis à un réacteur avec un flux de liquide à haute pression. Le contenu du réacteur peut être chauffé à une température et à une pression supercritiques, puis refroidi et ajusté à des températures et à des pressions sous-critiques. Des composés indicateurs peuvent être ajoutés et un mélange résultant peut être chauffé dans un autre réacteur puis analysé pour déterminer une quantité de matériau organofluoré présent dans l'échantillon.
PCT/US2024/018635 2023-03-06 2024-03-06 Systèmes et procédés d'analyse de fluor organique total WO2024186878A2 (fr)

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