Plasma-Enabled Liquid Filtration and Decontamination
20230278896 · 2023-09-07
Assignee
Inventors
- Scott G. Walton (Fairfax, VA, US)
- William A. Maza (Silver Spring, MD, US)
- Michael J. Johnson (Annapolis, MD, US)
- David R. Boris (Annandale, VA, US)
- Vanessa M. Breslin (Branford, CT, US)
- Grant C. Daniels (Burke, VA, US)
- Robert B. Balow (Mount Ranier, MD, US)
Cpc classification
C02F1/001
CHEMISTRY; METALLURGY
C02F1/283
CHEMISTRY; METALLURGY
International classification
Abstract
Apparatus and method for decontaminating both contaminated waters and sorbent filter media, either separately or simultaneously, in a single system. Contaminants in a liquid flowing through a reaction chamber are removed by first generating a plasma within the liquid in the chamber, with the contaminants being broken into smaller particles at the interfaces between the generated plasma and the liquid. The combined plasma-liquid solution is then passed through a solid filter, which captures the smaller contaminant particles to decontaminate the liquid. To decontaminate the filter media, plasma flows through the filter material without the presence of liquid, the plasma reacting with the filter material to remove contaminants previously adsorbed by the filter.
Claims
1. An apparatus for decontamination of a liquid, comprising: a reaction chamber having a first end and a second end opposite the first end; a hollow tube electrode and a solid electrode, each of the hollow tube and solid electrodes extending into the reaction chamber, a portion of each of the hollow tube electrode and the solid electrode being submerged within a liquid flowing through the reaction chamber; a power supply connected to the hollow tube electrode and to the solid electrode; and wherein a gas is introduced into the reaction chamber at the first end via the hollow tube electrode, the gas contacting both the hollow tube electrode and the liquid, a plasma volume being generated from the gas when a voltage from the power supply is applied across the hollow tube electrode and the solid electrode; wherein the liquid surrounds the plasma volume as it flows through the reaction chamber, the plasma causing parent species contaminant molecules in the liquid to break apart into daughter products comprising smaller molecular fragments as it contacts the liquid; wherein the liquid then passes through a filter situated between the plasma volume and an outlet from the reaction chamber; and wherein the parent species and daughter products in the liquid are adsorbed by the filter before the liquid is output from the reaction chamber via the outlet.
2. The decontamination apparatus according to claim 1, wherein the hollow tube electrode is situated at the first end of the reaction chamber and the solid electrode is situated at the second end of the reaction chamber.
3. The decontamination apparatus according to claim 1, wherein the hollow tube electrode is connected to a positive voltage lead from the power supply and the solid electrode is connected to a negative voltage lead from the power supply.
4. The decontamination apparatus according to claim 1, wherein the electrodes have ends that are planar disks with holes that allow liquid and gas, but not the filter material, to pass through the electrodes such that when power is applied to the electrodes, a plasma is generated in and around the filter material, exposing the liquid to the plasma while the liquid is flowing through the filter material.
5. The decontamination apparatus according to claim 1, wherein both the hollow tube electrode and the solid electrode are situated at the first end of the reaction chamber, the plasma being generated between the hollow tube electrode and the solid electrode.
6. The decontamination apparatus according to claim 1, wherein the gas comprises helium (He), xenon (Xe), argon (Ar), neon (Ne), or mixtures thereof
7. The decontamination apparatus according to claim 1, wherein the gas comprises oxygen (O.sub.2), nitrogen (N.sub.2), air, or mixtures thereof.
8. The decontamination apparatus according to claim 1, wherein the filter comprises granular activated carbon (GAC), ion exchange (IX) resins, or polymer fibers.
9. A method for decontaminating a liquid, comprising: providing a reaction chamber having a first end and a second end opposite the first end, the reaction chamber having a filter material situated within a filter cage situated near the second end; providing a hollow tube electrode and a solid electrode, each of the hollow tube and solid electrodes extending into the reaction chamber, a portion of each of the hollow tube electrode and the solid electrode being submerged within a liquid flowing through the reaction chamber; providing a power supply connected to the hollow tube electrode and to the solid electrode; introducing a gas introduced into the reaction chamber at the first end via the hollow tube electrode, the gas contacting both the hollow tube electrode and the liquid; and applying a voltage from the power supply to generate a plasma volume from the gas within the reaction chamber; wherein the liquid surrounds the plasma volume as it flows through the reaction chamber, the plasma causing parent species contaminant molecules in the liquid to break apart into daughter products comprising smaller molecular fragments as it contacts the liquid; wherein the liquid then passes through a filter situated between the plasma volume and an outlet from the reaction chamber; and wherein the parent species and daughter products in the liquid are adsorbed by the filter before the liquid is output from the reaction chamber via the outlet.
10. The method for decontaminating a liquid according to claim 9, wherein the gas comprises helium (He), xenon (Xe), argon (Ar), neon (Ne), or mixtures thereof
11. The method for decontaminating a liquid according to claim 9, wherein the gas comprises oxygen (O.sub.2), nitrogen (N.sub.2), air, or mixtures thereof.
12. The method for decontaminating a liquid according to claim 9, wherein the filter comprises granular activated carbon (GAC), ion exchange (IX) resins, or polymer fibers.
13. A method for regenerating a decontamination filter in a reaction chamber, comprising: providing a reaction chamber having a first end and a second end opposite the first end, the reaction chamber having decontamination filter material situated within a filter cage situated near the second end; providing a hollow tube electrode and a solid electrode, each of the hollow tube and solid electrodes extending into the reaction chamber; providing a power supply connected to the hollow tube electrode and to the solid electrode; introducing a gas into the reaction chamber at the first end via the hollow tube electrode; and applying a voltage from the power supply across the gas to generate a plasma within the reaction chamber; wherein the plasma passes through the filter material, the plasma causing contaminant molecules adsorbed by the filter material to be desorbed from the filter material and output from the reaction chamber.
14. The method for regenerating a decontamination filter in a reaction chamber according to claim 13, wherein the gas comprises ambient air, O.sub.2, H.sub.2, halogen gases, or reactive gases, either alone or in combination with a noble gas.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0026]
[0027]
[0028]
[0029]
[0030]
DETAILED DESCRIPTION
[0031] The aspects and features of the present invention summarized above can be embodied in various forms. The following description shows, by way of illustration, combinations and configurations in which the aspects and features can be put into practice. It is understood that the described aspects, features, and/or embodiments are merely examples, and that one skilled in the art may utilize other aspects, features, and/or embodiments or make structural and functional modifications without departing from the scope of the present disclosure.
[0032] The present invention provides a new approach to plasma-based remediation of liquids.
[0033] The apparatus and method of the present invention provides a means to plasma-treat both contaminated waters and solid sorbent media, either separately or simultaneously, in a single system.
[0034] The general concept described by this invention includes a sequential treatment of liquid flowing through the system whereby contaminants in a liquid can be removed by first exposing the liquid to a plasma and then passing the liquid through a solid filter.
[0035] The apparatus of the present invention can also be used to decontaminate the filter material in situ within the reaction chamber. In such a case, the plasma flows through the filter material without the presence of a liquid, with adsorbed contaminants previously removed from the liquid being desorbed as it reacts with the filter material.
[0036] Decontamination of a liquid in accordance with the present invention proceeds by first exposing the contaminated liquid to a plasma. The plasma serves to reduce or break apart the pollutant molecules (parent species) into smaller molecular fragments (daughter products) that may or may not be benign. The plasma can take many forms, such as charged particle (ion and electrons), reactive radicals (molecular fragments), excited species (metastable atoms), and photons, and all of these plasma species can interact with contaminates to chemically or energetically break apart the parent molecules. In some cases the plasma can also drive chemical reactions that convert the parent pollutant species or daughter products into benign molecules that can be output from the reaction chamber without harm to the environment. After its exposure to the plasma, the liquid flows through the filter region, where any remaining parent species or the daughter products can be adsorbed by the filtration media and removed from the water flow. The filter media can be engineered to adsorb a wide range of contaminants or to optimize adsorption of one or more specified contaminants.
[0037] When the intended operation is to decontaminate the filter material, the water flow is stopped and only the plasma is allowed to diffuse through the filter region. As the plasma passes through the filter media, active species produced in the plasma, such as charged particles (ion and electrons), reactive radicals (molecular fragments), excited species (metastable atoms), and/or photons interact with the filter media to desorb parent or daughter product adsorbates from the filter. The desorption process can be driven by either energetic or chemical pathways as appropriate for the desorption of one or more given contaminants. The gas, along with the desorbed contaminants, then exits the reaction chamber to ready it for another cleaning cycle.
[0038] This new concept in plasma remediation combines plasma exposure and filtration to destroy or remove contaminants in water, while also providing the ability to independently destroy or remove the contaminants adsorbed on solid sorbents used as filtration media. The latter enables in situ regeneration of the filtration material for repeated use.
[0039] The apparatus and method described in this disclosure provides a means to address the contamination of liquids by per- and polyfluoroalkyl substances (PFAS) or perfluorooctane sulfonate (PFOS) through a scalable process that combines direct plasma treatment with filtration to significantly reduce the level of PFAS contamination in both large and small water volumes.
[0040] The plasma can also be used to regenerate the filter media, in situ and without significant loss of material. The result is a more sustainable and less expensive approach that holds the potential for substantially increased decontamination efficacy.
[0041] Although the apparatus and method of the present invention were developed for the reduction of PFAS and PFOS substances in water, the principles behind the present invention can be applied to remediate other contaminants in water or other liquids, such as industrial dyes, pharmaceuticals, and herbicides.
[0042] In addition, although the apparatus and method of the present invention are described in the context of the exemplary configurations shown in
[0043] The block schematic in
[0044] While the geometry and scale of the apparatus setup in accordance with the present invention can vary according to needs, as illustrated by the schematic in
[0045] In accordance with the present invention, a gas enters reaction chamber 101 via gas flow inlet 105 and travels through hollow tube electrode 102. As the gas flows through the reaction chamber, a voltage from power supply 104 is applied across electrodes 102 and 103 and generates a plasma volume 109 from the gas within the reaction chamber. As described in more detail below, a liquid then enters the reaction chamber via inlet 106 and surrounds the plasma volume 109. As the liquid contacts and interacts with the plasma, the plasma causes parent species contaminant molecules in the liquid to break apart into daughter particles comprising smaller molecular fragments. The liquid then flows through the filter 107, where remaining parent species and the daughter particles are adsorbed by the filter before the liquid exits the reaction chamber via outlet 108.
[0046] The design of the treatment apparatus allows the system to be operated in two distinct modes. The first mode is a liquid reduction or decontamination mode, in which gas and contaminated liquid flow through the reaction chamber simultaneously while the plasma is running. The second mode of operation is designed to regenerate the filter material via plasma exposure.
[0047] In the first mode, gas and contaminated liquid flow through the reaction chamber simultaneously. The gas enters the reaction chamber through electrode 102 while the liquid enters through inlet 106 and passes over electrode 102, which is submerged within the liquid in the reaction chamber. The gas used can be selected according to the liquid to be decontaminated, the type and extent of contamination, and/or an extent of decontamination to be achieved. Exemplary gases that can be used for decontamination of a liquid in accordance with the present invention include the noble gases, e.g., helium (He), xenon (Xe), argon (Ar), or neon (Ne); in other cases, the input gas can include reactive gases such as oxygen (O.sub.2) or nitrogen (N.sub.2), air, or mixtures of any of these gases.
[0048] The presence of both the gas and the liquid in the reaction chamber produces a significant amount of mixing of the gas and the liquid such that when the voltage from the power source is applied to the electrodes, a plasma volume can be generated from the gas, where the plasma volume is surrounded by the liquid and is highly interactive with the liquid, producing a plasma-liquid surface interface where the plasma extends into the liquid and/or the liquid extends into the plasma. As the liquid interacts with the plasma at these interfaces, the pollutant molecules (parent species) are reduced and/or are broken apart into smaller molecular fragments (daughter products). In some cases, the plasma can also drive chemical reactions that convert the parent pollutant species or daughter products into benign molecules that can be output from the reaction chamber without harm to the environment.
[0049] The gas/liquid mixture containing the plasma volumes generated as described above then flows through the filter material. The combination of the initial creation of the plasmas within the liquid to break apart or convert the contaminants in the liquid, plus the subsequent filtering step of the liquid in accordance with the present invention enhances the removal of remaining parent species and/or daughter products from the liquid. The filtering step can be optimized using both adjustments in operating parameters and choice of filter material. For example, the filter material can comprise granular activated carbon (GAC), ion exchange (IX) resins, or polymers, depending on the liquid to be treated and the level and/or type of contamination. The filter can be a single stage or can be multiple stages, with each stage being the same material or different, with the materials and configuration of the filter being designed to capture predetermined types of contaminants and/or to provide a predetermined level of decontamination. In addition, in some cases, the liquid to be treated can be cycled multiple times through the reaction chamber to provide additional decontamination before treatment of the liquid is complete. Because the plasma acts to break apart the parent molecules into smaller daughter products and the filter material serves to adsorb either parent or daughter products, both the plasma and filtration media can designed to maximize the removal of contaminants such that the optimum contaminant removal rate can exceed the removal rate provided by each step separately.
[0050] The second mode of operation is designed to regenerate the filter material in situ via plasma exposure within the reaction chamber. In this second mode, the liquid flow is turned off and gas is introduced into the reaction chamber 101 through hollow electrode 102 in a manner as described above. The gas may be different in this filter-regeneration operational mode compared with the liquid treatment mode and chosen to most effectively regenerate the filter material. For example, the gas used in this filter regeneration mode can be ambient air, O.sub.2, H.sub.2, halogen gases, or reactive gases, either alone or in combination with a noble gas, depending on the contaminants to be removed.
[0051] When a voltage from power supply 104 is applied to the hollow and solid electrodes 102 and 103, a plasma is formed as described above. The reactive by-products in the plasma (e.g., O.sub.3, O, N, NO.sub.x, H, OH) penetrate the porous filter material such that all surfaces of the filter are exposed to the reactive species, with the adsorbates (e.g. PFAS or PFAS fragments) on the surface of the filter material being desorbed as the plasma interacts with the material. The gas with the desorbed particles is then output from the reaction chamber via the outlet.
[0052] Once the filter material is regenerated by its exposure to the plasma, the system can be switched back to the water-treatment mode of operation by re-engaging the liquid flow. In fact, switching between modes of operation is largely controlled by liquid and gas valves and requires no opening of the reaction chamber, unlike conventional decontamination systems, which require that the filter be removed from the chamber for cleaning and/or replacement, with the attendant risk of contamination of the environment due to leakage from the filter.
[0053] While the system is relatively straightforward in design, adding a filter or sorbent materials within a plasma system does require certain considerations, as the geometry of the device and plasma generation need to be tailored to accommodate the filter. The conductivity and structure of the filter material are important. Charging, particularly around structures on the surface of the sorbent materials can influence plasma operation. In the extreme, arcing can occur at these locations. Such phenomena can cause the plasma to transition to a different mode, which can produce high currents and temperatures, thus damaging system components and/or rapidly eroding the filter material.
[0054] The issue can be avoided by the appropriate selection of filter materials, support structures, or plasma power. Identifying or engineering filter material to meet these criteria can be a challenge. Good sorption characteristics must be balanced against good physical properties and response to plasma exposure. Fortunately, issues like mode transition and arcing can be prohibited using short duration high voltage pulses, operating at a favorable frequency. While this might seem counterintuitive to achieving rapid and efficient remediation, the results shown by the plot in
[0055] An example of the system's use to successfully destroy PFOS is shown by the plots in
[0056] As shown in
[0057] The plots in
[0058] The plot in
[0059]
[0060] Advantages and New Features
[0061] Plasma treatment and filtering are approaches to removing the contaminants in water. Combining these approaches in a single device and method—particularly for the destruction of PFAS in water—provides synergistic results. For example, destruction of PFAS molecules via plasma exposure can lead to small fragments of the parent molecule, including shorter chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkyl sulfonic acids (PFSAs), carbon dioxide, fluoride ions and sulfate ions. See K. Tachibana et al., “Reaction Process of Perfluorooctanesulfonic Acid (PFOS) Decomposed by DC Plasma Generated in Argon Gas Bubbles,” IEEE Trans. Plasma Sci. 2014, 42 (3), 786-793. As noted above, the work of Ross, et al. indicates that GAC performs poorly with shorter chain PFAS variants, while IX resins do better. See Ross et al., supra. As such, plasma treatment, when combined with IX resins, can serve to both rapidly and significantly reduce the amount of both long and short chain PFAS as well as the daughter fragments in the water being treated.
[0062] The ability to regenerate the filter material in situ also provides a distinct operational advantage. As stated above, typical non-thermal approaches involve the removal of PFAS using either an organic solvent rinse when treating hydrophobic media like GAC or high ionic strength salt solutions when treating IX resins. However, these approaches are ineffective at fully regenerating the sorption capacity of the matrices due to incomplete desorption, while also generating additional solvent waste. The use of thermal processes, on the other hand, result in the destruction of the material and the generation of harmful degradation products. In contrast, the present invention enables the regeneration of the filter without the need to remove or otherwise treat the filter, with the particles desorbed from the filter being output from the reaction chamber via the outlet. Importantly, the process is nondestructive and the materials do not have to be removed from the reaction chamber, which represents a real cost savings in terms of raw materials, labor, and down time.
[0063] Lastly, the electrode geometry and system operation associated with plasma production is optimized for treating liquids. In particular, the system is designed to produce one or more plasma volumes within the liquid, i.e., one or more plasmas surrounded by liquid, to ensure that the plasma terminates at the liquid interface. Moreover, the mixing of the liquid and gas produces a plasma volume with a very large plasma-liquid interface and small local liquid volume, which provides a large exposed liquid surface area and minimizes the penetration depth needed to treat the liquid. This combination of attributes enhances the delivery of active plasma species to the liquid and contaminants of interest, thus optimizing the remediation and destruction process.
Alternative Embodiments
[0064] Numerous alternative embodiments of the apparatus described herein may be employed. Such alternative embodiments can be configured to provide the best results for an intended decontamination application and/or the scale of the intended application.
[0065] Some such alternative embodiments of an apparatus for plasma-based decontamination of a liquid in accordance with the present invention are illustrated by the schematics in
[0066] The embodiment illustrated in
[0067]
[0068]
[0069]
[0070] In all of these embodiments, the gas is delivered through a powered electrode that is submerged in the liquid. The ground or negative electrode can assume a large variety of geometries, may or may not serve as the filter material holder, and may be located on either side of the filter material. When the filter material holder is not part of the circuit needed to drive plasma production (i.e. acting as an electrode), it can be made of insulating material. Alternatively, the filter material may be loaded between the two electrodes, where the electrodes can be perforated to accommodate liquid flow through the system. In addition, in all of the embodiments shown in
[0071] There are three general approaches to scaling the apparatus to accommodate larger throughput: increase liquid flow, increase the system diameter, or parallelize the process. Changing the system diameter would generally require that all components increase in diameter, but in practice, tube and electrode diameters need not scale at the same rate. Alternatively, a given volume of water could be treated faster by employing multiple apparatus in parallel. Such a configuration could be operated using a single sources for liquid, gas, and power. However, using a single power supply to drive multiple electrodes in parallel may require electrical ballasting to ensure equal distribution across all electrodes.
[0072] As noted above, the choice of filter material and/or configuration of the filter can also be tuned depending on the intended application. In many embodiments, the filter material can comprise granular activated carbon (GAC), ion exchange (IX) resins, or polymers, but any other suitable filter material or combination of materials can be used in single- or multi-stage filters to obtain a predetermined level of decontamination, depending on the liquid to be treated and the level of decontamination desired.
[0073] This new concept in plasma remediation combines plasma exposure and filtration to destroy or remove contaminants in water, while also providing the ability to independently destroy or remove the contaminants adsorbed on solid sorbents used as filtration media. Importantly, the combined use of submerged plasmas within the liquid as an initial treatment step to reduce or break up contaminants at the plasma-liquid interfaces, followed by filtration of the liquid to remove the contaminates increases the efficacy of remediation, and the ability to regenerate the filtration material in situ minimizes resource use. This combination of attributes leads to a more efficient and cost-effective approach to liquid remediation than is provided by decontamination systems in the prior art.
[0074] Although particular embodiments, aspects, and features have been described and illustrated, one skilled in the art would readily appreciate that the invention described herein is not limited to only those embodiments, aspects, and features but also contemplates any and all modifications and alternative embodiments that are within the spirit and scope of the underlying invention described and claimed herein. The present application contemplates any and all modifications within the spirit and scope of the underlying invention described and claimed herein, and all such modifications and alternative embodiments are deemed to be within the scope and spirit of the present disclosure.