Destruction of Perfluorosulfonic Acids (PFSAs) via Supercritical Water Oxidation

Abstract

Supercritical water oxidation (SCWO) is a destruction technology to quickly treat per- and polyfluoroalkyl substance (PFAS)-impacted groundwater, investigation derived waste, and other aqueous matrices such as landfill leachate and aqueous film forming foam. Laboratory-prepared and field-collected samples with inlet PFAS concentrations up to 50 parts per million were consistently destroyed to less than 70 parts per trillion for all PFAS, when running at the determined optimal operating conditions (≥600° C. and 3,500 pounds per square inch). We investigated the correlation between temperature and flowrate of the system, finding that reactor temperatures ≥450° C. destroys perfluorinated carbonic acids, but higher temperatures and specified conditions are necessary to destroy perfluorosulfonic acids. Using a higher density oxygen source also increases the throughput of a SCWO reactor, here up to 140 mL/min, without affecting PFAS destruction. Continuous 5-log reduction in the concentration of PFAS (99.999% destruction) is demonstrated for 3 hours at steady-state operation. The destruction efficiency is not impacted by the addition of co-contaminants such as petroleum and other organic hydrocarbons, and the SCWO process is successfully applied to waste streams without pretreatment. The treated effluent is largely comprised of complete combustion products including carbon dioxide, water, and the corresponding anion acids; hence, the treated liquid can be released back into the environment after neutralization.

Claims

1. A method of destroying perfluorosulfonic acids (PFSAs) in an aqueous composition, comprising: passing an aqueous composition comprising perfluorosulfonic acids (PFSAs) in a reaction vessel in the presence of an oxidant at a temperature of at least 550° C. and a pressure of at least 3350 psi and a residence time of at least 8 seconds.

2. The method of claim 1 wherein the temperature is at least 575° C.

3. The method of claim 1 wherein the temperature is at least 600° C.

4. The method of claim 1 wherein the pressure is at least 3350 psi.

5. The method of claim 1 wherein the residence time is at least 10 seconds.

6. The method of claim 1 wherein the residence time is in the range of 8 to 50 seconds.

7. The method of claim 1 wherein the reaction vessel has walls comprising a nickel alloy.

8. The method of claim 1 wherein the temperature is in the range of 550° C. to 650° C.

9. The method of claim 1 wherein the oxidant comprises H.sub.2O.sub.2.

10. The method of claim 1 wherein greater than 95% of the perfluorosulfonic acids are destroyed by the method.

11. The method of claim 1 wherein greater than 99% of the perfluorosulfonic acids are destroyed by the method.

12. (canceled)

13. The method of claim 1 wherein the amount of perfluorosulfonic acids in the aqueous composition are reduced at least 1000 fold by the method.

14. The method of claim 1 wherein the amount of perfluorosulfonic acids in the aqueous composition are reduced at least 10,000 fold by the method.

15. The method of claim 1 wherein the method reduces the amount of organofluorine compounds to below 70 parts per trillion.

16. The method of claim 1 wherein the perfluorosulfonic acids comprise PFOS.

17. The method of claim 1 wherein the method reduces the amount of organofluorine compounds by at least 10,000 fold.

18. The method of claim 1 wherein the method reduces the amount of organofluorine compounds by 10,000 fold to 100,000 fold.

19. The method of claim 1 wherein the method reduces the amount of organofluorine compounds by 100 fold to 10,000 fold.

20. The method of claim 1 wherein the aqueous composition comprises at least 100 ppm of perfluorinated sulfonates and the method decreases the perfluorinated sulfonates concentration by at least 10.sup.3 or 10.sup.6 or 10.sup.8, and up to about 10.sup.9.

21. The method of claim 1 wherein the aqueous composition comprises at least 0.5 ppm of perfluorinated sulfonates and the method decreases the perfluorinated sulfonates concentration by at least 10.sup.3.

22. The method of claim 1 wherein the aqueous composition comprises at least 0.5 ppm to 300 ppm of perfluorinated sulfonates and the method decreases the perfluorinated sulfonates concentration by at least 10.sup.3 or 10.sup.6 or 10.sup.8, and up to 10.sup.9.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0053] FIG. 1A plots the results of continuous testing at 3350 to 3500 psi (228 to 238 atm) and a residence time of 8 to 10 seconds,

[0054] FIG. 1B shows the PFAS Annihilator™ process flow diagram showing flow paths, sample heating, reactor location, and sample cooling prior to collection of the effluent samples at the sampling port.

[0055] FIG. 2. PFAS destruction with H.sub.2O.sub.2 as the oxidant is equivalent or superior to the PFAS destruction when using dissolved oxygen as the oxidant. System operating at 600° C., 3500 psi, and 50 mL/min.

[0056] FIG. 3. Effect of temperature and residence time on PFAS destruction. At 575° C., the lowest flow rate (60 mL/min) resulted in the highest reduction and 100 mL/min the second highest reduction. At 600° C., the highest flow rate (190 mL/min) showed the least reduction.

[0057] FIG. 4. Natural logarithmic ratio in the effluent PFAS concentrations at four residence times.

[0058] FIG. 5A. .sup.19F NMR spectra of PFOA and PFOS spiked influent and effluent samples. The x-axis is parts per million (ppm) and y-axis is relative intensity.

[0059] FIG. 5B. Concentration of PFAS and fluoride ions in the effluent overlaid with the reactor effluent temperature.

[0060] FIG. 6. Measured PFCAs, PFSAs, PFAS precursors/intermediates, and co-contaminants in treatments (a) Lab Sample, (B) Lab sample with co-contaminants spiked at low level, (C) Lab sample with co-contaminants spiked at high level, and (D) Field sample. The concentration of all PFAS compounds in the stream were less than 75 ppt after passing through the SCWO reactor.

[0061] FIGS. 7A-7B (Table 2) List of volatile organic compounds (VOCs) and total organic carbon analyzed.

[0062] FIGS. 8A-8E (Table 3) Concentration (ng/L) of PFAS entering and exiting the PFAS Annihilator™ SCWO reactor at different reactor operating temperatures and flowrates.

[0063] FIG. 9 (Table 4) PFAS Annihilator™ inlet and effluent concentrations (in ng/L) of PFAS at different time points during the two hours of steady state operation.

[0064] FIGS. 10A-10D (Table 5) PFAS and other co-contaminant concentrations (ppt) measured in separate tests performed on PFAS Annihilator™: (A) PFAS Spiked Lab sample; (B) PFAS Spiked Lab sample with the addition of low level TPH and VOC spikes; (C) PFAS Spiked Lab sample with the addition of high level TPH and VOC spikes; and (D) Field-collected sample.

DETAILED DESCRIPTION OF THE INVENTION

[0065] Operating conditions that destroy most perfluoroalkyl carboxylic acids (PFCAs) are lower than required for their sulfonated counterparts (PFSAs). The requirements for PFCAs are: temperature ≥450° C.; pressure ≥3350 PSI; residence time about 5 seconds although a shorter residence time and/or lower temperatures might also work for PFCAs.

[0066] In order to destroy perfluorosulfonic acids (PFSAs), additional heat and/or a longer residence time is required. A temperature of 550° C. or greater is needed to destroy appreciable amounts of the PFSAs; a temperature of at least 575° C. or greater is needed to destroy most of the PFSAs at the longer residence times; and a temperature of at least 600° C. or greater is needed to destroy most of the PFSAs at most of the tested residence times of 8 to 10 seconds. It is believed that within these temperature requirements, longer residence times will achieve destruction at the lower temperature range.

[0067] As shown in FIG. 1A, in continuous testing at 3350 to 3500 psi (228 to 238 atm) and a residence time of 8 to 10 seconds, it appears that temperatures above 450° C. to about 550° C. do not result in additional destruction of PFSAs. Surprisingly, however, we discovered that at temperatures above 550° C. or at least 575° C. or at least 600° C. was necessary for a substantial destruction of PFSA.

[0068] A preferred SCWO reactor design is a continuous or semi-continuous system in which the (typically pre-treated) PFAS-containing aqueous solution is passed into a SCWO reactor. Because solids may form in the SCWO reactor, it is desirable for the reactor to slope downward so that solids are pulled by gravity downward and out of the reactor. In some embodiments, the flow path is straight and vertical (0°) with respect to gravity; in some embodiments, the reactor is sloped with respect to gravity, for example in the range of 5 to 70° (from vertical) or 10 to 50° or 10 to 30° or 10 to 20° and can have a bend so that flow moves in a reverse direction to provide a compact device in which flow is consistently downward with respect to gravity. Preferably, the reactor vessel is a cylindrical pipe formed of a corrosion resistant material. Desirably, the pipe has an internal diameter of at least 1 cm, preferably at least 2 cm and in some embodiments up to about 5 cm.

[0069] Flow through the components of the SCWO apparatus at supercritical conditions should be conducted under turbulent flow (Re of at least 2000, preferably in the range of 2500 to 6000). Effluent from the SCWO reactor can flow into a salt separator under supercritical conditions.

Oxidants

[0070] The two tested feedstocks of reactant oxygen used in supercritical water oxidation for destruction of PFAS are oxygen gas (O.sub.2) and hydrogen peroxide (H.sub.2O.sub.2). In addition to, or alternative to, these two chemical species, other reactant oxygen sources or oxidizing agents could be added to destroy PFAS in the oxidation reactor. Other oxidants may comprise oxyanion species, ozone, air, and peroxy acids.

[0071] The preferred oxidant has a high oxygen density, such as hydrogen peroxide, which can be added in excess (for example an excess of at least 50% or at least 100% or in the range of 50% to 300% excess) and the excess hydrogen peroxide reacting to form dioxygen and water.

Additional Conditions

[0072] Any of the inventive processes can be characterized by one or any combination of the following: a PFAS-containing solution is mixed with a solution comprising 30 to 50 wt % H.sub.2O.sub.2 at a PFAS-containing solution:H.sub.2O.sub.2 solution weight ratio of preferably 30:1 to 70:1 wt % ratio or in a particularly preferred embodiment approximately 50:1 PFAS solution:H.sub.2O.sub.2. Desirably, sufficient or excess is present to oxidize all the components in the aqueous composition. In some embodiments, the PFAS-containing solution is passed through a SCWO reactor with a residence time of 60 sec or less, preferably 20 sec or less, 10 sec, or 5 sec or less, or 0.5 to 5 seconds. In reactors in which the PFAS is destroyed in supercritical conditions, the reactor volume is based on the volume comprising supercritical fluid conditions. A preferred reactor configuration is a continuous plug flow reactor. In some embodiments, the feed of concentrated PFAS is passed into an oxidation reactor a rate of about 50 mL/min; in some embodiments rate is controlled between 50 and 150 mL/min (at STP); this rate can be adjusted to obtain the desired conditions. The feed can include fuel and oxidant. Preferably, no external heating is required after start-up. In some embodiments, the PFAS-containing aqueous mixture (preferably after a concentration pretreatment) comprises at least 100 ppm of perfluorinated sulfonates and the method decreases the perfluorinated sulfonates concentration by at least 10.sup.3 or 10.sup.6 or 10.sup.8, and in some embodiments up to about 10.sup.9. Any of these conditions may be utilized or obtained in a mobile unit.

Examples

Chemicals and Reagents

[0073] Laboratory-prepared feeds were spiked with technical grade PFOA (98% purity), and PFOS (98% purity), along with lower amounts of PFBA, PFPeA, PFHxA, PFHpA, PFDA, PFUnDA, PFDoDA, 8:2 FTS, N-MeFOSAA, N-EtFOSAA, L-PFBS, and PFBS (Synquest Laboratories [Alachua, FL], Sigma Aldrich [St. Louis, MO] and Wellington Laboratories [Ontario, Canada]) (Table 1). Volatile organic compounds (VOCs; 1,1-dichloroethene, benzene, tetrachloroethene, toluene, and trichloroethene) (SPEX CertiPrep, Metuchen, NJ) and diesel fuel (Turkey Hill, OH) were added as co-contaminants. Final concentrations in the inlet feed were determined through PFAS, total organic carbon (TOC), and VOC analysis. The full list of PFAS and organic compounds evaluated are shown in Tables 1 and Table 2, respectively, but only detected compounds are presented in the figures for visual clarity. Optima™ grade methanol (≥99.9% purity) (Sigma Aldrich), and certified American Chemical Society grade acetone (≥99.5% assay) and ammonia (7 N solution in methanol) (Fisher Scientific [Pittsburgh, PA]) were used to clean the reactor between trials. Hydrogen peroxide (H.sub.2O.sub.2) from Sigma Aldrich was used as the oxygen source, and monobasic sodium hydroxide (NaOH) from Sigma Aldrich was added to the process to neutralize the effluent stream. Deionized (DI) water was produced in house via a two-tank deionizing system in parallel, installed and maintained by AmeriWater (Dayton, OH).

TABLE-US-00001 TABLE 1 Definition of PFAS grouping and acronyms and the detection limit in water. Detection Limit Abbreviation Analytes CAS RN (ng/L) Perfluorinated Carboxylic Acids (PFCAs) PFBA Perfluorobutanoic acid   375-22-4 0.14 PFPeA Perfluoropentanoic acid  2706-90-3 0.31 PFHXA Perfluorohexanoic acid   307-24-4 0.19 PFHpA Perfluoroheptanoic acid   375-85-9 0.16 PFOA Perfluorooctanoic acid   335-67-1 0.18 PFNA Perfluorononanoic acid   375-95-1 0.26 PFDA Perfluorodecanoic acid   335-76-2 0.16 PFUnA Perfluoroundecanoic acid PFDOA Perfluorododecanoic acid   307-55-1 0.18 PFTrDA Perfluorotridecanoic acid  72629-94-8 0.15 PFTeDA Perfluorotetradecanoic acid   376-06-7 0.25 Perfluorinated Sulfonic Acids (PFSAs) PFBS Perfluorobutanesulfonic acid   375-73-5 0.13 PFPeS Perfluoropentanesulfonic acid  2706-91-4 0.67 PFHxS Perfluorohexanesulfonic acid   355-46-4 0.11 PFHpS Perfluoroheptanesulfonic acid   375-92-8 0.2 PFOS Perfluorooctanesulfonic acid  1763-23-1 0.19 PFNS Perfluorononanesulfonic acid  68259-12-1 0.46 PFDS Perfluorodecanesulfonic acid   335-77-3 0.17 Precursors/Intermediates PFOSA Perfluorooctanesulfonamide   754-91-6 0.27 NMeFOSAA N-Methylperfluorooctane  2355-31-9 0.56 sulfonamido acetic acid NEtFOSAA N-Ethylperfluorooctane  2991-50-6 0.49 sulfonamido acetic acid 4:2FTS 4:2 fluorotelomer sulfonic acid 757124-72-4 0.14 6:2FTS 6:2 fluorotelomer sulfonic acid  27619-97-2 1.36 8:2FTS 8:2 fluorotelomer sulfonic acid  39108-34-4 0.22 Note: CAS No. chemical abstract service registry number

SCWO Reactor

[0074] The bench-scale PFAS Annihilator™ is comprised of a tubular reactor heated by an Accurate Thermal Systems (Hainesport, NJ) sand bath. A tube-in-tube heat exchanger was used to preheat the feed and recover heat after the reaction. Additional cooling of the reactor effluent was performed using a cooling drum supplied with potable water. A custom-designed gas-liquid separator was used to separate the treated aqueous effluent from the generated vapor. The feeds, oxidant, and neutralization solutions were pumped through the PFAS Annihilator™ utilizing Shimadzu (Columbia, MD) LC 20-AP preparative pumps. Pressure was monitored throughout the system with in-line Swagelok (Solon, OH) 6,000 psi pressure gauges. Pressure was maintained in the system utilizing a Tescom (Elk River, MN) 4,000 psi back pressure regulator. Effluent pH was measured using a Sensorex (Garden Grove, CA) TX100 in-line pH meter. Temperatures were measured with in-line Type K thermocouple probes (Omega, Norwalk, CT). A schematic of the PFAS Annihilator™ used to evaluate the destruction of PFAS is shown in FIG. 1B. The temperature readings were output to a BrainChild PR20 data logger (CAS Dataloggers, Chesterland, OH). Due to the high temperatures and pressure operating conditions and the generation of hydrofluoric acid, a high nickel alloy (Alloy 625) that is highly resistant to corrosion was used for all hot and pressurized components of the system. No glassware or other laboratory ware is used anywhere in the system or in the handling of samples destined for PFAS analysis to mitigate the potential for PFAS loss to glassware.

Laboratory Samples

[0075] Laboratory-prepared inlet samples were composed of PFAS, petroleum hydrocarbons, and/or VOCs prepared in DI water, followed by sonication for at least 1 hour. Anions can be analyzed using U.S. EPA Method 300 and Modified EPA 300.0 and 300.1. TOC can be analyzed using U.S. EPA Method 9060A; VOCs analyzed by U.S. EPA Method 8260C; Target PFAS by LC-MS/MS QSM v 5.3 B-15; and non-target PFAS by LC/ToF/MS.

Field Samples

[0076] Upon receipt, all field samples were analyzed for PFAS, VOCs, TOC, and anions as described above. The TOC and PFAS concentrations were used to calculate an appropriate oxidant dosing for the field sample. The field sample detailed in this report was run through the PFAS Annihilator™ without any preprocessing or preparation.

SCWO Operating Conditions

[0077] At the beginning of each run, the SCWO reactor was allowed to reach its equilibrium temperature (±10° C.) running DI water at 3,500 psi (±200 psi). The oxidant solution was prepared to achieve ≥100% excess oxygen in the system, calculated assuming complete combustion of the TOC and/or total target PFAS in the feed. Either the liquid oxidant (H.sub.2O.sub.2) or the dissolved gaseous oxygen was pumped via a secondary Shimadzu LC-20AP preparative pump into the system upstream of the reactor at 3,500 psi along with the feed/sample stream. A neutralization solution (NaOH) was prepared such that an effluent pH of 5 to 7 was achieved while ensuring the neutralization flow did not exceed 7% of the total system flowrate. The feed and oxidant were introduced into the PFAS Annihilator™ at their specified flowrates after the system temperature stabilized. The vapor stream, primarily consisting of carbon dioxide and excess oxygen, was separated from the aqueous stream in a gas-liquid separator and sampled by C18 cartridges and impingers prior to being discharged into the laboratory hood. The liquid effluent samples were collected from the sampling port as labeled in FIG. 1B.

[0078] After each run was completed, the system was immediately flushed with DI water and/or low concentration oxidant. After cooling, the system was rinsed with DI water, methanol, and then again with DI water. For runs with a high concentration of PFAS or where operating conditions were not optimal for PFAS destruction, ammonia in methanol and/or acetone was also used to clean the system.

Sample Analysis

[0079] All samples were analyzed for PFAS at Battelle's accredited laboratory, using isotope dilution liquid chromatography tandem mass spectrometry (LC/MS/MS). Transformation byproducts formed during SCWO were analyzed using Waters Acuity I-class UPLC Sample Manager coupled to a Quadrupole time-of-flight mass spectrometer, TripleTOF/MS 5600 (AB Sciex, Framingham, MA) at Battelle's Laboratory. The aqueous influent, effluent, and equipment blanks, and gaseous effluents (methanol extracts of C18 cartridges and impinger) were investigated for transformation byproducts. Details on all analytical methods for PFAS are described in the Supporting Information. To characterize fluorine changes, influent and effluent samples were analyzed using .sup.19F-Nuclear Magnetic Resonance (NMR) spectroscopy at Battelle's Laboratory. The .sup.19F NMR spectra were obtained with a Bruker AVANCE NEO 500 MHz NMR spectrometer equipped with a broadband observe probe with gradients in a mixture of water and deuterium oxide as the solvent. Chemical shifts were reported relative to CFCl.sub.3 (0 part per million [ppm]). Fluoride was also commercially evaluated by anion analysis using U.S. EPA Method 300. TOC and VOCs were commercially analyzed using U.S. EPA Methods 9060A and 8260C, using samples collected in volatile organic analysis vials preserved with phosphoric acid and hydrochloric acid, respectively.

Data Analysis

[0080] The relative change of PFAS, fluoride, TOC, and VOCs was determined by comparing the inlet and effluent concentrations of the system. Equations for percent destruction and defluorination can be found in Equation 1 and Equation 2. This analysis assumes that little, if any, accumulation of compounds occurred in the SCWO system for accurate representation of compound destruction/production. The reported effluent concentrations are those directly measured exiting the reactor without correcting for dilution from the addition of the oxidant or neutralization solutions. This provides an accurate representation of the reactor discharge. Since the feed sample is diluted by less than 15% when using H.sub.2O.sub.2 as the oxidant, the concentration changes reported are representative of the reactor performance and are not due to significant dilution of the feed stream.

[00001]$\begin{array}{cc}\%\mathrm{destruction}=\frac{\mathrm{effluent}\mathrm{concentration}\mathrm{of}\mathrm{PFAS}\left(\frac{\mathrm{ng}}{L}\right)}{\mathrm{inlet}\mathrm{PFAS}\mathrm{concentration}\mathrm{as}\mathrm{organofluorine}\left(\frac{\mathrm{ng}}{L}\right)}\times 100& \mathrm{Equation}1\end{array}$$\begin{array}{cc}\%\mathrm{defluorination}=\frac{\mathrm{effluent}\mathrm{inorganic}\mathrm{fluoride}\left(\frac{\mathrm{ng}}{L}\right)}{\mathrm{inlet}\mathrm{PFAS}\mathrm{concentraiton}\mathrm{as}\mathrm{organofluorine}\left(\frac{\mathrm{ng}}{L}\right)}\times 100& \mathrm{Equation}2\end{array}$

To simplify the data presentation when the concentration of many PFAS are being reported, the PFAS are classified as PFCAs, PFSAs, and precursors/intermediates as defined in Table 1, and the raw concentration values of each measured PFAS compound are then tabulated.

Results and Discussion

[0081] Using the laboratory-spiked inlet samples, the effects of oxidant type, temperature, and residence time on the SCWO destruction of PFAS were evaluated.

Impact of Oxidant Type on PFAS Destruction

[0082] Two oxidant sources, dissolved oxygen in water and H.sub.2O.sub.2, were used to provide at least 100% excess oxygen in independent tests. In the initial investigation, H.sub.2O.sub.2 provided equivalent or superior destruction of all measured PFAS, including PFCAs (PFBA, PFPeA, PFHxA, PFHpA, and PFOA) and PFSAs (PFBS, PFPeS, PFHxS, PFHpS, and PFOS) compared to dissolved oxygen as the oxidant source when operating at 3,500 psi and 600° C. (FIG. 2). Both oxidants caused a similar 4 to 6 log reduction in the concentration of the total effluent PFAS relative to the total inlet concentration of 11.3 ppm. In both cases, only the two compounds having the highest concentrations in the inlet (PFOA and PFOS) were still present at over 100 ppt in the effluent; The other measured compounds were not detected or were detected at less than 3 ppt. H.sub.2O.sub.2 has about 1,000× higher oxygen density than oxygen dissolved in water at 100 psi, dramatically reducing the required volume of oxidant added to the feed stream and reducing the combined reactor volumetric flowrate by ˜5×. This greatly reduces the volume of water that must be heated when operating the reactor, reducing energy requirements and cost of operation. Other researchers have also observed accelerated oxidation performance with H.sub.2O.sub.2 compared to oxygen on organic contaminants. Ren, M. et al. Supercritical water oxidation of quinoline with moderate preheat temperature and initial concentration. Fuel 236, 1408-1414 (2019). This is due to the high activation energy of O.sub.2 oxidation and the slow conversion of O.sub.2 and H.sub.2O that requires three steps to produce OH radicals as shown in Equation 3 through Equation 5. Alternatively, the decomposition of H.sub.2O.sub.2 to OH radicals is direct (Equation 5). Due to the equivalent or improved destruction of PFAS when using H.sub.2O.sub.2 in this study and in the literature, H.sub.2O.sub.2 is used as the oxidant source for the remaining tests.

CF.sub.3(CF.sub.2).sub.nRH+O.sub.2.fwdarw.CF.sub.3(CF.sub.2).sub.nR.Math.+HO.sub.2.Math.  Equation 3

CF.sub.3(CF.sub.2).sub.nRH+HO.sub.2.Math..fwdarw.CF.sub.3(CF.sub.2).sub.nR.Math.+H.sub.2O.sub.2  Equation 4

H.sub.2O.sub.2.fwdarw.20H.Math.  Equation 5

Impact of Residence Time and Temperature on Performance

[0083] The combination of elevated temperature and residence time provides enough energy to overcome the activation energy to cleave the carbon-fluorine bond to degrade PFAS to produce carbon dioxide (CO.sub.2) and hydrofluoric acid (1F). A generic reaction is shown in Equation 6 using PFOA as an exemplar PFAS.

C.sub.8HF.sub.15O.sub.2+7H.sub.2O.sub.2.fwdarw.15HF+8CO.sub.2  Equation 6

To determine the optimal operating conditions, influent and effluent concentrations of PFAS were measured at four flowrates in 25° C. increments from 450° C. to 625° C. At least 85% of total PFAS were destroyed under all tested conditions. Between the operating temperatures of 450° and 525° C., the reactor operated in this ≥85% destruction efficiency regardless of flowrate. A similar observation was made by other researchers studying the batch-scale reactions of PFOS, where the highest PFAS destruction was observed at 500° C., and the reaction at this temperature was independent of the residence time; therefore, it was concluded that temperature is the key parameter for PFAS destruction (Pinkard, B. R., Shetty, S., Stritzinger, D., Bellona, C. & Novosselov, I. V. Destruction of perfluorooctanesulfonate (PFOS) in a batch supercritical water oxidation reactor. Chemosphere 279, 130834 (2021)). However, the current study expanded to higher temperatures using a flow through system. This setup shows that, further elevated temperatures allowed the reaction to destroy >99% of PFAS. Destruction of PFAS is inversely dependent on residence time or indirectly dependent on the reactor flowrate.

[0084] At temperatures ≥525° C., slower flowrates show improved PFAS destruction. A slower flowrate also achieves maximum destruction at lower temperatures compared to reactions run at higher flowrates. At 550° C. the slowest tested flowrate (60 mL/min) showed an additional 1- to 2-log reduction in the effluent PFAS concentration than seen at any of the other tested flowrates (100, 140, and 190 mL/min). At 575° C. the 60 mL/min flowrate achieves the maximum PFAS destruction (about 5-6 log reduction). Increasing flowrates at this operating temperature (575° C.) reduced PFAS destruction efficiency. Further increasing the temperature allowed higher flowrate streams to also achieve the maximum PFAS destruction. However, the reactor was unable to maintain a temperature of 625° C. at 190 mL/min due to the energy transfer required to heat the high influent flowrate. Figure summarizes these data. The concentration of all 24 PFAS from each of two sequential samples collected at each set of conditions is shown in Table 3 (FIG. 8). Interestingly, the non-sulfonated PFAS (PFCAs) showed complete defluorination at all temperatures and flowrates evaluated, while the sulfonated acids (PFSAs) required a higher temperature and residence time to be defluorinated. The degradation of the PFCAs makes up nearly all the destruction seen at temperatures ≤500° C.

Estimated Reaction Kinetics

[0085] The reactor flowrates were converted to residence times to estimate the reaction kinetics for the degradation of PFAS within the reactor. The residence time at each data point shown in Figure is unique because under supercritical conditions, the reaction temperature has a notable impact on density, leading to variable residence times for a consistent volumetric flowrate. The reaction rates were estimated using the PFAS compounds whose concentrations were above the limit of quantitation (LOQ) for all four tested residence times, which only included PFSAs (all PFCAs were destroyed under all test conditions). A reactor operating temperature of 575° C. was used for these calculations because it shows the greatest disparity in the destruction efficiency of PFAS over the tested flowrate range. At lower or higher temperatures, the reaction is either not at all impacted by the residence time, or there is only one data point that is not at either the maximum (C.sub.t/C.sub.0≅1E-5) or minimum (C.sub.t/C.sub.0≅1E-1) destruction, meaning that there are not sufficient data points sampled to properly estimate the kinetics at those temperatures. Figure indicates first order reaction kinetics at 575° C. and provides rate constants (k) of 0.51, 0.49, and 0.48 for PFOS, PFHxS, and PFHpS, respectively.

The first-order reaction equation for PFSA destruction is shown in Equation 7. Although not

ln(A)=ln(A.sub.0)−kt  Equation 7

shown in Figure, shorter chain PFSAs and all PFCAs proceeded to non-detect (ND) quickly, which prevented an accurate rate calculation for those compounds (Table 4).

Steady State Operation

[0086] To determine the startup and steady-state operation of the PFAS Annihilator™, the system was operated for 3 hours with effluent samples collected every 20 minutes. These samples were analyzed to measure the loss of target PFAS and the generation of inorganic fluoride. The concentration of PFAS in the effluent decreased by ˜4 orders of magnitude within 20 minutes of introducing the feed solution, while the effluent fluoride concentration increased dramatically. The concentration of PFAS was reduced by another order of magnitude after another 20 minutes of operation, while the fluoride remained at nearly the same level (FIG. B). This is expected as there is a diminishing return in total generated fluoride as the concentration of PFAS undergoes further log reductions. The large increase in fluoride concentration in the effluent suggests mineralization of PFAS by defluorination during the SCWO treatment. In addition, .sup.19F NMR analysis of influent and steady-state effluent samples further supports this finding. There is an increase in inorganic F peak in effluent spectra, and disappearance of organofluorines (F attached to carbons) resulting from defluorination of PFAS (FIG. 5A). Although .sup.19F NMR spectra represents a qualitative analysis, disappearance of the organofluorine peaks further demonstrates the complete defluorination of PFAS.

[0087] The reactor showed a slight 15° C. decrease in the effluent temperature for the first 40 minutes of operation, which was recovered and even slightly elevated by 60 minutes of continuous operation. By 60 minutes of continuous operation, all measured parameters had reached a steady value and remained constant for the remaining 120 minutes of testing, suggesting about a 1-hour time to steady state for the PFAS Annihilator™ (FigureB). Additionally, the status of the reactor is well summarized by the temperature reading; When the reactor effluent temperature has re-equilibrated after the introduction of sample, the SCWO system is operating at steady state and is achieving optimal PFAS destruction.

[0088] Throughout this steady-state period, the total effluent PFAS concentration remained below 50 ppt, which is six orders of magnitude lower than the total inlet PFAS concentration of 22.8 ppm (99.9998% destruction). The most concentrated compound in the inlet (PFOA) was decreased by nearly 7 orders of magnitude from 12.3 ppm to 3.83 ppt. The inlet and effluent concentrations for fluoride and for all 24 measured PFAS are provided in Table 5.

[0089] Comparing the total inlet and effluent fluorine, a total of 72.6% of the total inlet fluorine (largely contained in the PFAS) is detected and quantified in the effluent as ionic fluoride. While this may indicate that some fluorine is accumulating within the reactor, the reactor was rinsed with water after testing to collect any fluorine sorbed onto the reactor surfaces. While some fluoride was detected (0.77 mg/L), this totaled less than 0.5% of the total inlet fluorine, suggesting that the reaction byproducts are not accumulating within the reactor. The total target PFAS measured in the post run water rinse was also low (27.0 ppt), further suggesting that undestroyed PFAS is not adhering to or building up on the reactor walls. This data suggests that neither PFAS nor the reaction product, fluorine, are accumulating within the reactor. In addition, the reactor surface residuals were collected and analyzed via energy dispersive spectroscopy (EDS) and x-ray diffraction (XRD) and show that there is no fluorine detected on these surfaces, further supporting the idea that PFAS are destroyed rather than accumulated or sorbed onto the reactor surfaces. Additional effort is underway to better understand the movement of fluorine through the reactor.

Effect of Co-Contaminants on PFAS Annihilation

[0090] The PFAS Annihilator™ has been demonstrated to greatly reduce the concentration of PFAS in laboratory-spiked samples (Figure, Figure, FigureB); However, environmental samples are much more complex and can have a number of additional co-contaminants. In many of the Department of Defense (DoD) sites impacted by AFFFs due to fire-fighting or fire-training activities, it is common to find VOCs and total petroleum hydrocarbons (TPH) commingled with PFAS contamination. To evaluate the practicality of applying this technology to environmental remediation, a laboratory-spiked sample was prepared consisting of PFAS, TPH (low and high concentration), and VOCs (low and high concentrations). The low-concentration spiked sample was found to contain ˜1,200 ppt of total organic contaminants, and the high-concentration spiked sample was found to contain ˜7,400,000 ppt of total organic contaminants. The measurable TOC concentrations are shown in the bottom row of Figure, and detailed data of all analytes is provided in Table 5. The results show that the destruction of PFAS is largely unaffected by the addition of organic co-contaminants when compared to the laboratory sample that was only spiked with PFAS (FIG. A) and that the total concentration of co-contaminants also decreases (FigureB and C). This proves that SCWO is effective for co-contaminant treatment along with PFAS destruction. The total PFAS concentrations and the sum of PFOA and PFOS measured in the low-concentration effluent sample (FigureB) and the PFAS-spiked lab sample (FIG. A) were 15.72 ng/L and 1.23 ng/L, respectively, compared to 31.46 and 28.37 ng/L in the absence of co-contaminants. Overall, the destruction efficiency of PFCAs, PFSAs, and PFAS precursors was not affected by the presence of co-contaminants (Figure and Table 5). This confirms that complexity of the feed stream does not alter the destruction efficiency of PFAS, and the results demonstrate effective destruction of co-contaminants in the PFAS-impacted IDW streams. The effluent vapor was similarly analyzed for PFAS. This analysis yielded no detectable levels of any of the 24 target PFAS, confirming that the influent compounds are being destroyed rather than escaping the system as a gas.

[0091] The individually detectable co-contaminants were found to decrease to undetectable levels in both the low- and high-concentration spiked samples (FigureB and C), and all target organic compounds (and TOC when detected) decreased. This is an expected result as SCWO processes are not specific to breaking carbon-fluorine bonds. Carbon-carbon bonds are also expected to oxidize under the operating conditions of the PFAS Annihilator™.

Demonstration on an AFFF-Impacted IDW Sample

[0092] As yet another proof of concept demonstration, an AFFF-impacted IDW sample was run through the PFAS Annihilator™. The field-collected sample with an initial total target PFAS concentration of 4.9 ppm was run directly through the SCWO reactor without any preprocessing, and a similar destruction efficiency of PFAS was achieved as the laboratory PFAS-spiked sample (FIG. D). The resultant effluent total PFAS concentration was 10.2 ppt and the sum of PFOA and PFOS measured at 1.5 ppt showing six orders of magnitude reduction in PFAS (Table S6), demonstrating the PFAS Annihilator™ as a viable technology to destroy high concentrations of PFAS in AFFF-impacted IDW. Although there was a slight increase in the measured concentration of two VOCs from the influent to the effluent, both concentrations are below the method quantitation limit and may not be accurate. Another interesting finding was a decrease in dissolved fluoride as the field sample passed through the reactor (Table 5). This may be associated with the dramatic change in ion solubilities as water transitions from the sub to supercritical state. Methods to collect this precipitating material are underway and will allow further evaluation of this hypothesis.

[0093] In all trials (PFAS spiked, PFAS and co-contaminants spiked, and field samples), PFCA, PFSA, and PFAS precursors/intermediates show a similar level of destruction regardless of the complexity of the feed (Figure A-D). The total summation of measured PFAS concentration in effluent samples in each of the laboratory and field samples was ≤75 ppt (ng/L) with no individual PFAS analyte concentration remaining higher than 70 ppt for any collected effluent sample. The influent and effluent PFAS concentrations for each of the samples presented in Figure are tabulated in Table 5, which highlights the similarities in the effluent PFAS concentration that are achieved by the PFAS Annihilator™ from disparate inlet samples, demonstrating that the complexity of the feed stream does not alter the destruction of PFCAs, PFSAs, PFAS precursors/intermediates, or organic co-contaminants.

[0094] Although no pretreatment was required for any of the tested samples and no clogging was observed in these tests, the underlying tubular reactor may be prone to clogging from samples with high concentrations of dissolved solids. The built-in pressure and flow monitors would have deviated from their steady-state operational conditions if appreciable build up were occurring. During long-term operations, processing much larger samples for weeks at a time, the potential reactor clogging could be mitigated with the use of inline devices (e.g., a supercritical salt trap) or modified reactor designs to remove salts and other compounds that precipitate out of solution at supercritical conditions.

Identification of Byproducts

[0095] Aqueous influent, effluent, and equipment blanks, and gaseous effluents (methanol extracts of C18 cartridges and impinger) were investigated for transformation byproducts using LC-qToF/MS analysis. Greater than 99% destruction of PFOA and PFOS was achieved in the effluent, hence no longer chain PFAS were detected in the samples analyzed.

[0096] Some unidentified short-chain byproducts were formed and found to elute early on the total ion chromatography (TIC) chromatogram. These are very low-level findings relative to the targeted compounds, which were unquantifiable without analytical standards and were not consistently seen on every run. These data suggest that SCWO completely destroyed PFAS, instead of partial mineralization, which agrees with our previous data from the liquid effluents and reactor surfaces.

Environmental Implications

[0097] The PFAS Annihilator™ tested here is demonstrated as a promising technology for the destruction of PFAS and other common co-contaminants typically found at AFFF-impacted fire training sites. This research presents optimization of the reaction conditions for the complete destruction of PFAS. The oxidant type (O.sub.2 and H.sub.2O.sub.2), temperature (450-625° C.), flowrate (60-190 mL/min), and time to reach steady-state conditions were studied. The best operating conditions (≥600° C. and ≤100 mL/min or 625° C. and ≤140 mL/min) using H.sub.2O.sub.2 as the oxidant destroyed PFAS in laboratory-spiked solutions with initial concentrations ranging from 5 to 50 ppm to below 70 ppt levels in the resultant effluent. The optimized technology was then applied to three inlet sources (PFAS spiked with and without co-contaminants and a field sample) where it successfully reduced PFAS of different chemistries, chain lengths, and precursor presence by up to 6 orders of magnitude. This preliminary data and the impact of operational changes is valuable in upscaling SCWO systems for the destruction of PFAS in contaminated sources for environmental remediation. These data suggest that the destruction of PFAS using SCWO is independent of the oxygen source used in the reactor and that higher temperatures can be used to maintain destruction efficiency while increasing throughput.

[0098] Many technologies for the treatment of PFAS-impacted IDW rely on separation techniques, which transfer PFAS from one media to another and therefore generate PFAS-concentrated secondary waste streams (e.g., sorbents and ion exchange regenerated solvent concentrate, reverse osmosis reject, nanofiltration) that require further treatment or disposal. Incineration poses several challenges such as off-site transportation, concerns on the incomplete combustion of byproducts, high energy requirements, immediate release of combustion products into the environment, and cost of operation. See Stoiber, et al. “Disposal of products and materials containing per- and polyfluoroalkyl substances (PFAS): A cyclical problem,” Chemosphere 260 (2020). As no destruction methods are readily available for the long-term effective management of PFAS-impacted IDW and these secondary waste streams, SCWO provides an effective approach. SCWO is an energy intensive process, but much of the expended energy can be recaptured through heat exchangers in a well-designed system. SCWO is also not appropriate for thick slurries (>50% solids) as they do not pump well through a reactor. The SCWO process demonstrated here is capable of directly processing a PFAS-impacted field sample, and the effluent can be released to the environment after confirmatory analysis. Further demonstration is on-going to prove pilot- and full-scale field deployments of the PFAS Annihilator™ at AFFF-impacted sites, landfill leachate, as well as the destruction of stockpiled AFFF concentrates.