Multi-catalyst water treatment system

Abstract

A water treatment system includes a vessel configured to receive water containing at least one contaminant into its interior. Within the vessel, there are a plurality of cathodes and anodes arranged at a ratio of two anodes per cathode. A power supply is connected to both the cathodes and anodes, The system further includes a light source, which can include an infrared (IR) light source, an ultraviolet (UV) light source, or a laser light source.

Description

MULTI-CATALYST WATER TREATMENT SYSTEMCROSS-REFERENCE TO RELATED APPLICATION

[0001] The present application claims priority of U.S. Provisional Application No. 63 / 654,717, filed on May 31, 2024, which application is incorporated by reference herein in its entirety.BACKGROUND

[0002] Per- and polyfluoroalkyl substances (PFAS) are a group of man-made chemicals that have been in use since the 1940s. They are often referred to as “forever chemicals” due to their persistence in the environment. PFAS are found in many consumer products like cookware, food packaging, and stain repellants. They are also used in industrial applications, including stain-resistant and water-resistant fabrics and carpeting, cleaning products, paints, and firefighting foams.

[0003] PFAS are widely used, long-lasting chemicals, components of which break down very slowly over time. Because of their widespread use and their persistence in the environment, traces of PFAS may now be found in plants, animals, food, people, and in the environment. PFAS and be found in water, air, fish, and soil.

[0004] The sources of PFAS contamination are varied. Manufacturing processes and waste storage and treatment sites release PFAS into the air, soil, and water. Industrial facilities such as petroleum stations and terminals, chemical manufacturers, commercial printers, plastics and resin manufacturing sites, paint and coating manufacturers, semiconductor manufacturers, makers of metal products and electrical components, and electroplating and polishing are among the facilities that are known or suspected of using PFAS. Landfills and waste disposal facilities, along with sewage and waste treatment plants, are other common sources of contamination. Firefighting foam is another source of PFAS in the environment.

[0005] The challenges that PFAS present to drinking water sources are significant. PFAS are very soluble in aquatic systems, making them difficult to remove from various water sources. The chemical nature of PFAS makes biodegradation, photolysis, and hydrolysis more challenging.

[0006] Scientific studies have shown that exposure to some PFAS in the environment may be linked to harmful health effects in humans and animals. PFAS exposure over a long period of time can cause cancer and other illnesses that decrease quality of life or result in death. PFAS exposure during critical life stages such as pregnancy or early childhood can also result in adverse health impacts.

[0007] Contamination of drinking water by various PFAS can pose challenges for states and communities, and some have called for regulation to establish enforceable standards for these substances. This has resulted in a move to establish concentration limits for several well- researched PFAS chemicals in drinking water to reduce PFAS exposure for approximately 100 million Americans served by public drinking water systems. This is a significant step towards addressing the challenges posed by PFAS to drinking water sources. However, the complexity and persistence of these chemicals mean that ongoing research and regulation will be necessary to fully understand and mitigate their impact on our environment and health.

[0008] PFAS are challenging to remove from the environment and drinking water due to their strong carbon-fluorine bonds. This chemical stability means PFAS do not degrade easily under natural environmental conditions or through conventional water treatment processes. Their persistence allows them to accumulate in the environment and in the bodies of living organisms.

[0009] Moreover, the vast number of PFAS compounds, each with different chemical properties, adds to the challenge, as treatment methods may need to be tailored to effectively remove specific PFAS compounds from contaminated water sources. The persistence and complexity of PFAS contamination necessitate ongoing research and development of more effective and efficient removal methods to protect public health and the environment.

[0010] Numerous approaches for water treatment exist, including those of the inventor’s earlier work set forth in US2013 / 0075312, “Water Purifier,” US2017 / 0203986, “Water Purification System,” US11572297, “Biopolymeric Water Treatment,” and US11965893, “Biopolymeric Water Treatment,” the contents of which are all incorporated by reference in their entireties. However, for the reasons set forth above, further water treatment processes are needed for treatment of PFAS.BRIEF DISCLOSURE

[0011] A water treatment system includes a vessel configured to receive water containing at least one contaminant into its interior. Within the vessel, there are a plurality of cathodes andanodes arranged at a ratio of two anodes per cathode. A power supply is connected to both the cathodes and anodes, and a light source, which can be an infrared (IR) light source, an ultraviolet (UV) light source, or a laser light source, is included.

[0012] In examples, the system includes a waveform generator connected between the power supply and the electrodes, providing electrical energization at a frequency of at least 15 kilohertz. The light source can emit light at various wavelengths, including IR light between 780 nm and 1060 nm, UV light within the UV-C band, and laser light between 435-1400 nm. The electrodes are arranged in concentric rings or repeating groups of anode-cathode-anode, with the cathodes made of graphite and the anodes of titanium. The power supply operates within a range of 24-120 volts and 25-100 amps. The system also includes a gas source and a piping assembly to release dispersed bubbles of gas, such as air, ionized air, oxygen, ozone, or nitrogen, into the water. The gas can be ionized air provided by an ionizer, and the piping assembly extends into the vessel to release the bubbles. The system may have multiple vessels, with the gas bubbles released into the water within each vessel. A gas outlet and a fraction outlet are positioned at the top of the second vessel, within a collection bell. A filter connected to the gas outlet removes substances from the exiting gas. The filter media can include desiccant, activated carbon, redox alloys, zeolite, metal organic frameworks, covalent organic frameworks, ethylene glycol, and methanol. The filtered gas can be redirected to the gas source or the first vessel. The system also includes a laser oxidation system with a pulsed fiber laser, which subjects the foam fraction of contaminants to laser oxidation under negative pressure. The gas emitted from this process is directed to the filter.

[0013] In still further examples, the system has a source of biopolymer and / or geopolymer, which is provided to the water as it flows between vessels, forming a homogeneous mixture and adsorbing contaminants. The system includes a collection funnel at the bottom of the vessel and an ultrasound emitter to emit sound waves into the vessel. The water received in the vessel may contain an additive of geopolymer and / or cationic biopolymer.

[0014] A method of water treatment involves receiving contaminated water within the vessel, providing electrical energization to the electrodes, and energizing the light source to expose the water to light energy. The light source can be IR, UV, or laser, emitting light at specific wavelengths. The method also includes providing diffused bubbles of gas to the vessel and venting the gas, with at least two steps performed concurrently.BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 depicts an example of a water treatment system in cross-section.

[0016] Figure 2 is a further cross- section of the example of the water treatment system.

[0017] Figure 3 depicts a gas treatment vessel for the water treatment system.

[0018] Figure 4 depicts a further example of the water treatment system including a gas treatment system.

[0019] Figure 5 is a flow chart depicting an example of a process of water treatment.

[0020] Figure 6 depicts a further example of an arrangement of concentric electrodes.

[0021] Figure 7 is a system diagram that depicts an additional configuration of the water treatment system.DETAILED DISCLOSURE

[0022] The present disclosure relates to treatment of water. In particular, the present disclosure relates to the treatment of water for the removal of contaminants including PFAS chemicals.

[0023] The water treatment systems as described herein may be configured to perform in a batch treatment setting or in an in-line or continuous flow treatment. In a batch treatment arrangement, a vessel or vessels are filled with contaminated water. One or more of the treatment systems as described herein are arranged in the vessel and operate to treat the contaminated water. A batch treatment system may include multiple treatment modalities within a single vessel, such modalities may be operated simultaneously or sequentially. In still further examples, multiple vessels with different treatment modalities may be used to sequentially treat water passing from the one vessel to the next. The water to be treated is held in each vessel for a predetermined exposure / treatment time based upon the contaminants in the water and the treatment modality. In an in-line or continuous flow treatment, the treatment modalities a e aligned with the water conduit and the volumetric flow rate of the water controlled to achieve the intended exposure / treatment time for each of the treatment modalities.

[0024] While the description provided herein is generally made with respect to a hatch or vessel arrangement, it will be recognized that this disclosure similarly applies to an in-line system as well.

[0025] The water treatment system 100 described herein includes the use of electrolysis alone or in combination with one or more additional treatment modalities. Figure 1 depicts an example of a water treatment system 100 as a cross-sectional view of an exemplary water vessel 10 with an arrangement of cathodes 12 and anodes 14 arranged circumferentially about the vessel 10. The cathodes 12 and anodes 14 are arranged in a 1:2 ratio with an anode 14 to either side of each cathode 12. Thus, in the arrangement, two anodes 14 separate each cathode 12. The anode and cathode are made of specific materials that increase the rate of hydrogen and oxygen production and / or to perform a specific reactive function within the medium in the reactor vessel. The cathodes are exemplarily graphite and the anodes are exemplarily titanium. A current is passed between two or more electrodes. The contaminated water between the two or more electrodes is exposed to direct or alternating current. This electrical current can be used to oxidize minerals, elements, compounds, and / or contaminants within the water.

[0026] It will be recognized that other materials may be used for the cathodes and / or anodes as well while remaining within the scope of the present disclosure. The electrodes may include, but are not limited to graphite, graphene, iron, nickel, zinc, magnesium, aluminum, copper, manganese, molybdenum, diamond, boron, boron nitride, boron sulfide, carbon nitride, ceramic, titanium, ruthenium, stainless steel, carbon steel, quartz, or persulfate. While a graphite - titanium system example is described above, additional non-limiting examples, include one or more iron cathodes and / or anodes to add iron ions into the contaminated water to react with H2O2 to create an electro Fenton reagent. Titanium anodes and / or cathodes may create TiCh electrons that increase photochemical oxidation in combination with UV and / or IR wavelengths of light as will be described in further detail herein. The presence of aluminum in pure, composite, or alloy form in one or more cathodes and / or anodes may productively react with fluoride from the PFAS structure in the degradation of PFAS chemicals.

[0027] While the inventor has discovered that this arrangement of the cathodes and anodes provides a surprising benefit, it is further contemplated that other arrangements of cathodes and anodes including other cross-sectional shapes of rods, cones, plates, wire, and / or wire mesh may be used. Figure 6 provides an additional exemplary layout of concentric rings ofelectrodes 12, 14 as disclosed herein. The electrodes are exemplarily powered by two 24V, 1000W, 40A 110 / 220V to DC regulated universal transformer power supplies 16. Portions of the disclosure will be in non-limiting reference to this example. However, it will be recognized that other specific power supplies and specifications may be used, along with similar modifications to other components. In another non-limiting examples, these power supplies were increased to 48V, 1200W, 25A power supplies; 120V 50A power supplies; or 120 V 100A power supplies with associated transformers.

[0028] Waveform generators 18 are connected to the electrodes 12, 14. Waveform generators 18 are exemplarily dual channel waveform generators. The channels may be programmed to each provide a different energy signal. One or both of the waveform generators may be a 15MHz waveform generator and exemplarily produce a first channel of 15MHz Lorenz wave with an amplitude of 10V, offset of 5V and a duty cycle of 90% and a second channel of 15MHz sine pulse wave with an amplitude of 10V, offset of 5V and a duty cycle of 90%. One or both of the waveform generators may be 70MHz dual channel waveform generator and exemplarily produce a first channel of 65MHz Gauss wave with an amplitude of 9V an offset of 5.5V and a duty cycle of 90% and a second channel of 70MHz square pulse wave with a 9V amplitude, 5.5V offset and 90% duty cycle. These are non-limiting examples and other waveform generators and waveforms may be used. Additionally, it will be recognized that the waveform generators 18 and resulting outputs are contemplated to be modified while remaining within the scope of the present disclosure for use with the larger power supplies described above.

[0029] Waveform generators 18 may further operate to provide an ultrasonic component to the treatment provided by the electrodes. This may be advantageous to use the waveform generator in this manner as opposed to a dedicated ultrasonic emitter and horn style flow cell. The waveform generator 18 enables the use of multiple specific programmed ultrasonic frequencies onto the anode and cathode network of the system. Longitudinal, compressional, or pressure ultrasonic waves, transverse or shear ultrasonic waves, carrier, burst, surface or Rayleigh waves, Lamb, or flexural plate waves are all examples of waves that may be used in addition to the waveforms as previously described and in frequency ranges exemplarily between 15kHz -10GHz.

[0030] Operation of the electrodes 12, 14 powered by the waveform generators 18, treat the contaminated water in the vessel 10 with electrochemical oxidation. The electrical currentcauses the H2O to separate into hydrogen and oxygen. Hydroxyl (-OH) radicals are formed along with free hydrogen and oxygen. Some hydrogen and oxygen separated in this reaction reform to create hydrogen peroxide (H2O2). The H2O2 formation is used to create Fenton, non-Fenton, and Fenton-like oxidative reactions to break down the contaminants. Hydrogen, oxygen, and H2O2 also act as catalysts for UVC, infrared, laser light, and electrolysis reactions as described in further detail herein. Creating H2O2 within the system when treating water has a compounding oxidative effect when combined UVC, IR, lasers, and reactive media as described in further detail herein. Later, the H2O2 may be decomposed into water and oxygen.

[0031] As alluded to above, the system may further include one or more light sources (20, 22, 24). These light sources emit light which has been found to photoreact with the ions in the water produced by the above electrolysis to promote breakdown of PFAS and other contaminants in the water. The light sources (20, 22, 24) may include some or all of an ultraviolet band C (UVC) light source 24, an infrared (IR) light source 20, and a laser light source 22.

[0032] The UVC light source 24 exemplarily produces UVC spectrum light (100-280nm) in further examples the wavelengths are between 200-280nm. In one example as tested, UVC light is provides at a wavelength of 254nm.

[0033] The IR light source 20 may provide light in wavelengths between 780nm and 1mm. This may include e.g. near IR (780nm - 1400nm), medium IR (1400nm-3000nm), and far IR (3000nm - 1mm). In tests, 810nm, 830nm, 850nm, and 1060nm were used, however other wavelengths within the ranges provided above are contemplated within the present disclosure.

[0034] The laser light source 22 emits monochromatic and coherent light, exemplarily in the visible spectrum, recognizing that the UVC light source and the IR light source, in examples, may emit monochromatic and coherent light within those wavelength bands. In an example tested, a 12V 520 nm 1W laser light source was used. Laser light sources may be continuous or pulsed and may further be gas or liquid cooled. Laser light sources in the range of 435-590 nm are contemplated within the scope of the present disclosure. In other non-limiting examples, wavelengths between 435-1400 nm may be used. One tested example used 1080 nm wavelength light. More specifically 500-565 nm, 500-520 nm, or 520-565 nm wavelengths may be used. In non-limiting examples, copper vapor, argon, helium neon, or krypton lasers may be used producea wavelength within one or more of these ranges. In other examples, 22V l -3kW laser light sources by be used, for example with a wavelength between 435-1400 nm.

[0035] The light from the one or more light sources noted above reacts with the ions in the water created by the electrolysis to oxidize the contaminants in the water, oxidizing contaminants to release oxygen, carbon, hydrogen, fluoride, potassium, sodium, calcium, magnesium, silicon, sulfur, lithium, (base, transition, and rare earth elements) from feedstock sources, soils in the water, sea water, wastewater, etc. The redox photoreactions destroy pathogens including but not limited to; E Coli, Giardia, MERSA, MERS, COVD-19, Anthrax, Ebola, Influenzas, Mold, Fungus, Legionella, Cryptosporidium, Candida, etc.

[0036] The laser light as described above exemplarily creates hydroxyl radicals. The laser light photochemically oxidizes elements and compounds via electron transfer. The laser source can be operated on a constant duty, pulsed, or programmed cycle. Pulsed laser light on oxide-based electrodes can create magnetic fields. The wavelengths and power including combinations thereof can be determined according to the input chemistry and intended outcome.

[0037] In a tested example, green wavelengths (e.g. 500-570 nm) of laser light were used. In other examples, light having a wavelength above 1000 nm may be used, with one example being a wavelength of 1080 nm. A specific and / or broad spectrum of light, light sources, ultrasound, electricity with varying voltage, amperage, and wattage, as well as additives (ionized air, minerals, etc.) can be used to treat / oxidize / mineralize almost any type of material.

[0038] Implementations of the presently disclosed water treatment system may include a variety of options and configurations as described herein. Electro oxidation from the operation of the electrodes 12, 14 as described provides a catalyst to enhance electrolysis and reactivity / oxidation and / or absorption of UVC, IR, laser energy, and / or ionized air from the other treatment modalities in the system as described herein. Applying an electrical current to the anode and / or materials in proximity to the UVC source 24 produces available electrons from the cathode material that act as photocatalysts when exposed to the UVC light energy. Applying an electrical current to the anode and / or cathode materials in proximity to the IR light source 20 produces available electrons that act as photocatalysts when exposed to the IR light energy. Applying an electrical current to the anode and / or materials in proximity to the laser source 22 produces available electrons that act as photocatalysts when exposed to the laser source light energy. Applying UVC and infrared light simultaneously in proximity or separately in sequentialstages has a compounding photochemical oxidation effect. Applying infrared and laser light simultaneously in proximity or separately in sequential stages has a compounding photochemical oxidation effect. Applying UVC and laser light simultaneously in proximity or separately in sequential stages has a compounding photochemical oxidation effect. Applying UVC, infrared, and laser light simultaneously in proximity or separately in sequential stages has a compounding photochemical oxidation effect. Injecting bipolar ionized air adds positively and negatively charged ions into the system which increases the oxidation and / or catalysis within the catalyst system.

[0039] Figure 2 is a cross section of the vessel 10 in a plane perpendicular to that of Fig. 1 and showing the water treatment system 100. The cathodes 12, anodes 14, IR source 20, laser source 22, and UVC source 24 all extend lengthwise along a major axis of the vessel 10. It will be recognized that the vessel 10 may be oriented in a variety of manners (e.g. horizontally or vertically) while remaining within the scope of the present disclosure. The vessel 10 includes an inlet 26 and an outlet 28. Flow through the inlet 26 and the outlet 28 may be controlled by valves 30. Operation of the valves 30 may close the outlet 28 to fill the vessel with contaminated water through inlet 26. Once filled, the combined electrolysis and photo treatment described above is performed. When a predetermined treatment time has been met, the electrodes and light sources are turned off and the valve 30 opened to release the treated water through the outlet 28.

[0040] Figure 3 depicts an example of a pretreatment and separation stage 200 which may be used to treat contaminated water prior to the water treatment system 100. The pretreatment stage 200 includes a vessel 32. The vessel 32 has an inlet 34 for contaminated water and a water outlet 36. The vessel 32 also includes a gas outlet 38 and a foam fraction outlet 40. The vessel 32 further includes a piping assembly 42 that extends throughout the interior of the vessel 32 towards a bottom end of the vessel, for example, opposite from the inlet 34. The piping assembly includes a plurality of holes which produce diffused bubbles of gas 44 upwards through the vessel 32. The gas may be ionized air, oxygen, ozone, or other gasses as may be recognized from the present disclosure and are provided to the piping assembly 42 from a gas source 46. The gas source 46 may include ionization of ambient air which is non-corrosive and does not form carcinogenic byproducts. The ionizers may include, but are not limited to 110- 120V AC micro needle plasma ion generator or 120V brush / sweep plasma ion generator.However, there are many AC and DC ion generators available and are considered to be within the scope of the present disclosure.

[0041] The diffused bubbles of gas 44 from the piping assembly 42 travel upwards through the contaminated water in the vessel 32 towards the gas outlet 38. Buoyant fractions of e.g. algae, proteins, foam, fats, oils, or suspended solids, travel upwards with the gas into a collection bell 48 at the top of the vessel 32. In the collection bell 48, the buoyant fractions are separated from the gas which continues through the gas outlet 38. An internal wall of the collection bell 48 helps to separate the foam fraction from the gas and collect the foam fraction in proximity to the foam fraction outlet 40. In examples, the gas exiting the collection bell 48 through the gas outlet 38 can be further treated, as is described in further detail with respect to Figure 7. This gas can be collected, filtered and subsequently reused in the system to increase or sustain oxidation reactions. It will be recognized that in various examples, the gas outlet 38 and the foam fraction outlet 40 may be a single outlet or may be two separate outlets from the collection bell 48. In an example wherein a single outlet is used the gas and foam fraction may be further separated downstream of the outlet from the collection bell 48.

[0042] The upward gas flow concentrates contaminants which may include some PFAS (surface active foams) into the collection bell 48 where they can be removed / pumped / vacuumed into a separate vessel for disposal and / or destruction. Examples of which will further be described herein with respect to Fig. 7. This concentrated and isolated fraction of contaminants could be collected for disposal or can be oxidized, destroyed, or demineralized, using the technologies and methods as described herein or using another form of contaminant treatment technology.

[0043] A negative pressure is applied to the foam fraction outlet 40, to help collect the fractionated substances from the collection bell 48 and divert the fractionated substances for collection or additional treatment. In examples, the water treatment system 100 receives at the inlet 26 (Fig. 2) the water exiting the pretreatment stage 200 from water outlet 36. In further examples, depending upon the intended outcome or use and physical properties of the fraction removed from the foam fraction outlet 40, this fraction may be subjected to treatment as described above with respect to the water treatment system 100 or other processing or filtering as may be recognized from the present disclosure. Such examples will be described in further detail with respect to Fig. 7.

[0044] Figure 4 provides a further example of the water treatment system 300, recognizing that the water treatment system 300 may include all of the water treatment system 100 as previously described and combine it with the pretreatment stage 200. Like reference numerals between those two descriptions are used to denote like and previously described components. Contaminated water enters through the inlet 26 where the water is subjected to the electrolysis and light treatments as described above while the gasification with ionized air / oxygen / ozone or other gas removes a fraction of substances from the water. It has been observed that the electrolysis and light treatments as described above may create salts and / or other precipitates as the contaminant chemicals are broken down. In still further examples, the perturbation of the water with the gas bubbles may decrease the localized density of the water, further causing solid contaminants to sink. Thus a collection funnel 52 is positioned at the bottom of the vessel 50, wherein the precipitates and / or other solids are collected. A gate 56 may be positioned at the bottom of the funnel 52 and opened to expel the precipitates through an outlet 54, for example, for collection.

[0045] In the examples described above, gas, including, but not limited to bipolar ionized air (micro needle, sweep, etc.), ozone, nitrogen, argon, CO2, hydrogen, filtered or unfiltered ambient air, etc. This gas is diffused through the vessel after injection to ensure maximum contact of the gas with the contents of the reaction vessel. Air can be treated to remove atmospheric nitrogen and airborne contaminants prior to ionization, ozonation, and / or air injection. An example where this may be utilized is in water treatment or a chemical manufacturing process where the inclusion of nitrogen is undesirable. An example where ambient nitrogen or additional nitrogen would be included / added / injected into the system is in an Ammonia production process. Water is split into O2 and H and H is reformed with nitrogen to form ammonia much like the Haber Bosch process. Similarly, other gases, liquids, elements, can be injected into the vessel to produce other elements, precursors, compounds during the electrolysis and photo treatment. Carbon dioxide may be used in production of formate or hydrogen. Carbon monoxide may be used in the production of carbon dioxide. Glycerol may be used in the production of hydrogen. Methanol may be used in the production of hydrogen. Other compounds may be added to the system to increase oxidation of substances or the formation of other elements, precursors, or compounds.

[0046] Negatively charged ions from the ion generator may be used alone or paired with negatively charged mincrals / formulas as exemplarily disclosed in in US 11572297 and to increase anionic clotting or coagulation and to induce intended chemical reactions with the system. In such an example, the contaminants may clump and / or coagulate, and may be collected in the funnel 52. Positively charged ions from the ion generator may be used alone or paired with positively charged mineral s / formulas as exemplarily disclosed in in US 11572297 to increase cationic flocculation and to induce a reaction within the system. In such an example, the contaminants may settle or floc for collection in the funnel 52. In still further examples, the ion generator(s) provide negatively charged ionized air and positively charged ionized air for simultaneous or sequential application within the system.

[0047] Figure 5 is a flow chart that depicts an example of a process 400 for treating contaminants in water. It will be recognized that some of the process steps may be performed at the same location (e.g. in a batch processing arrangement), or may be performed simultaneously. Examples of the process may perform each step sequentially with a different vessel or portion of a continuous flow system. Still further examples of processes as presently disclosed may include reordered steps, or more or fewer steps than those as shown in Fig. 5.

[0048] At 502 the ionized air, for example from the gas source 46 is applied to the contaminated water. As described above, the ionized air begins an oxidation process and also can operate to separate a foam fraction containing numerous contaminants from the water. At 504, the contaminated water goes through electrolysis as described above with a plurality of cathodes and anodes at a ratio of 1:2. Phototreatment occurs at 506 with UVC and 508 with IR. As described above, the phototreatment may further include the use of lasers. Optionally, at 510, in a vessel or batch process, the contaminated water is subjected to pressure. The pressure may be at least lOOpsi. In a sealed vessel, the pressure may be increased by either the addition of pressurized gas, for example, the ionized air from 502. In other examples, the oxidation reactions occurring within the vessel may increase the pressure within the vessel, if the excess pressure is not vented off. It will be recognized that all of the preceding steps may occur within a single vessel and may occur simultaneously, or concurrent with some or all of the preceding steps. At 512 the processed water may be filtered to remove any salts or precipitates created as a byproduct of the reactions. Once filtered, the processed water may be released for a further use or as treated effluent into a waterway.

[0049] Figure 7 is a system diagram of a further example of a water treatment system 700 incorporating the components as described above. The contaminated water is pumped through inlet 34 into the vessel 32 of the gas treatment system 200. As described above, a gas source 46 provides gas to a piping assembly within the gas treatment system 200 to produce an upflow of diffused gas bubbles within the vessel 32. The gas provided by the gas source 46 may be ionized air, oxygen, ozone, or other gasses as may be recognized. In one example, the gas is ionized air, as described above which may be produced by filtering and ionizing ambient air. In an example, the gas source 46 is an air pump that receives ambient air (and / or filtered gas from the gas filtration and collection system described herein), one or more filters to remove contaminants from the ambient air, and one or more ionizers as described above to create positive and / or negative ions in the air / gas before it is delivered to the vessel 32.

[0050] The gas treatment system 200 uplifts and concentrates some contaminants from the water into the collection bell 48. The gas outlet 38 vents the gas from the gas treatment system 200 to one or more filters 58. The one or more filters may be a plurality of filters, although it will be recognized that one, some, or all of the described filters may be included in the one or more filters 58, and are not necessarily limiting on the filters which may be used. In an example, four filter stages are provided. A first filter stage is a desiccant which operates to remove moisture from the gas. The desiccant may exemplarily be silica gel or activated alumina, or others as may be recognized by the present disclosure. A second filter stage is activated carbon and / or redox alloys to remove contaminants that are entrained within the gas. These contaminants may include but are not limited to fluorine, VOC’s, or heavy metals. It will be recognized that other filter materials may be used for this stage and / or may remove other contaminants in the stage as well. A third filter stage is for the purpose of CO2 absorption, this may include, but is not limited to carbon compositions, activated carbon, zeolites, metal organic frameworks (MOF), or covalent organic frameworks (COF). A fourth filter stage is for the purpose of hydrogen absorption. This filter stage may include ethylene glycol and / or methanol. These filter stages are exemplary and may be arranged in other combinations or orders. The filtered gas may be returned to the gas source 46 for reuse within the system as noted above. In other examples, the filtered gas may be used in subsequent treatment stages, for example in combination with the electrolysis treatment system 100. In other examples, it may be capturedfor uses apart from within the water treatment system 700. Sequestered carbon or hydrogen from respective filter stages may be subsequently reclaimed for other uses as well.

[0051] The foam fraction of the contaminants in the collection bell 48 is pulled away from the collection bell 48 for example by way of a peristaltic pump or source of negative pressure. The foam fraction of the contaminants are directed to a laser oxidation system 60. In an example a pulsed fiber laser of 50 W or greater, up to and including 5000 W, power is directed at a target area through which the foam fraction of the contaminants are passed. One example of a laser may be RFL-C1500-CE laser available from Raycus Fiber Laser Technologies Co. Ltd. The target area may be dimensioned to match a beam width of the laser. Exemplary and non-limiting beam widths may be between 10-300 mm. In some examples, this treatment, may be sufficient to neutralize this fraction of contaminants, which may then be collected for disposal. In other examples, the treated fraction may further be passed to an electrolysis system 100 as described above. In a still further example, the laser oxidation system 60 may be combined with the electrolysis system 100 as described above, and the foam fraction treated with this combined system. In examples, depending upon the liquid content of this fraction, water may be added to the fraction to promote adequate flowing through the electrolysis system 100. Vapors emitted from this treatment may be collected and directed to the one or more filters 58 as described above. In other examples, an in- situ arrangement of the electrodes may be used to treat a fraction without additional water, for example with an array of electrodes as described above, surrounded by the fraction of the contaminants for treatment. It will be recognized that such arrangement would be an example of a batch processing.

[0052] Returning to the gas treatment system 200, the water fraction from the gas treatment system 200 leaves through outlet 36. In an optional stage, biopolymer and / or geopolymer may be added to the water fraction after leaving the gas treatment system 200. The biopolymer / geopolymer treatment may be as explained in US 11572297, as already referenced. In one example, the biopolymer / geopolymer material is a combination of one or more of aragonite, bentonite, and zeolite. In still further examples the material further includes chitosan. This treatment material may adsorb thereon at least one contaminant from the water fraction. The treatment material may be added to the flow of the water fraction from the gas treatment system 200, or a separate vessel (not depicted) may be used to expose the contaminated water to the biopolymer / geopolymer material, agitate such combination, and separate the water from the treatment materialand the at least one contaminant adsorbed thereon. A non-limiting example of such a process is described in US 11572297. In another example, the biopolymer I geopolymer material is added to the flow of the water fraction where the flow and filling of a subsequent electrolysis system 100 with the combined water fraction and biopolymer / geopolymer material forms a homogeneous mixture of the water fraction and the biopolymer / geopolymer material.

[0053] The electrolysis system 100 operates as described above to treat the water with electrical current, initiating the Fenton and Fenton like reactions to break down the contaminants in the water. Additionally, as described above, this system exemplarily incorporates photolysis treatments as well. It has been recognized that the addition of the biopolymer I geopolymer material in these examples, may enhance the water treatment by providing reagent materials for oxidative reactions, while also coagulating the treatment material and some contaminants and / or the byproducts of contaminant oxidation for settlement and collection at the outlet 54, which clarifies the remaining water fraction, resulting in improved photolysis of remaining contaminants in the water fraction by exposure to the light energy from the IR 20, laser 22 and UVC 24 light sources. As depicted and described with respect to Fig. 4, the electrolysis system 100 may further be connected to the gas source 46 and or the filtered gas output from the one or more filter 58 to provide subsequent gas treatment of the water in this stage, in conjunction with the electrolysis and photolysis treatments described above. It will be recognized that in such examples may include a collection bell (not depicted) and the connections to the one or more filter 58 and laser oxidation system 60 as previously described.

[0054] The treated water leaves the electrolysis system 100 and may be contaminant free, hi other examples, further processing like RO filtering, water softening, or a further stage of biopolymer / geopolymer filtration may be used depending upon the final use or destination of the treated water.

[0055] In an example of treating drinking water, graphite anodes and titanium cathodes were used. The cathodes in this system work as electron donors. The titanium cathodes produce TiO electrons which work as available photocatalysts to react with the UVC in the system. This enhances the photochemical oxidation of contaminants. In one example of the drinking water treatment process, the water enters a chamber where it is exposed to UV, IR, lasers, ultrasound, electrical current, ionized air, and ozone. Everything can be done in ambient conditions, apart from the energy introduced from the above. When the vessel is sealed, such treatments mayincrease the pressure therein and the created pressure may he used as an added advantage to processing for contaminant removal.

[0056] In an example of wastewater treatment, graphite anodes and iron cathodes were used to produce Fe electrons and create an electro Fenton reaction within the water. This pretreatment step helps reduce contaminants and clarify the water prior to the photo treatment including but not limited to UV. Wastewater, landfill leachate, mining tailings, biosolids, PF AS, etc. may require electro-oxidation, ionized air injection, ozonation, ultrasound, PH adjustment, and biopolymeric water treatment (as exemplarily described in US 11572297) may be used to remove / oxidize / demineralize / clarify the water prior to UV, IR, and / or Laser treatment. As reported in the Appendix A of U.S. Provisional Application No. 63 / 654,717, which is incorporated by reference in its entirety, the process described above neutralized a variety of PFAS chemicals in the samples tested.

[0057] The redox system can be used to demineralize or break down persistent and emerging compounds including, but not limited to, PFAS, TCE, PCB’s, 1,4 Dioxane, Pesticides, Pharmaceuticals, Microplastics, Pathogens, Treatment Resistant Microbes, etc. The redox system includes ultraviolet light, infra-red light, how powered lasers, ultrasound, electromagnetic energy, and an electrical current created by one or more electrodes. (Including but not limited to) ionized air (micro needle, sweep, etc.), ozone, nitrogen, argon, CO2, filtered and unfiltered ambient air, etc. is injected into the reaction cell.

[0058] Further examples of the system can be used to treat sludges and slurries such as wastewater sludge, biosolids, soil slurries, etc. to remove contaminants. In one example, PFAS may be removed from wastewater sludge prior to spreading the biosolids therefrom on farm fields as fertilizer.

[0059] Examples of the system provided herein can be used to decrease or eliminate one or more contaminating factors in water, air, fluids, sludges, and slurries treatment, for example, BOD, COD, TSS, TDS, heavy metals, pathogens, ammonia, nitrogen, phosphorous, fluoride, chlorine, halogens, hydrogen, sulfur, VOC’s, PFAS, TCE, PCB’s, 1,4 Dioxane, Pesticides, Herbicides, Fungicides, Pharmaceuticals, Microplastics, Algae Blooms, Algal Toxin, Dyes, Petroleum Products, VOC’s.

[0060] Examples of the system can break the carbon fluorine bond of PFAS in long and short chains. Breaking PFAS chains releases CO2, hydrogen, fluoride, ammonium, and sodium.Minerals generated from this process can be filtered out. The process splits H2O into hydrogen and oxygen, and creates hydroxyl radicals.

[0061] Further examples can demineralize and refine produced petroleum, or the used / extracted water from oil and gas exploration and production. This may include harvesting the base, transition, and rare earth elements present in the treated substance and producing clean water and or upgrading the petroleum or bitumen to light, sweet oil products. Produced petroleum water and frac water, but also mining wastewater, coal fly ash wastewater, landfill leachate may be treated in this manner to mineralize ionic salts, minerals, and metals out of the water. Minerals including, but not limited to: magnesium, calcium fluoride, lithium, cobalt, boron, silver, rare earth elements, aluminum, platinum, nickel, titanium, vanadium, manganese, tellurium, niobium, tin may be removed in this manner.

[0062] The electrolysis process adds heat to the treated water. This heat can help with other oxidation reactions. Using higher amperage in the electro-oxidation process creates higher heat in the system. Oxidative catalysts for oxidizing / breaking down contaminants and long compounds like plastics and PFAS. Heat can also be very useful when reforming other elements or compounds such as ammonia, CO2, formic acid.

[0063] In examples with gas injection and / or oxidative reactions, with a closed vessel, for example with the gas, fraction, and water outlets closed, the pressure within the vessel will increase, furthering oxidation and degradation of certain contaminants and elements and or formation of elements depending on the input chemistry. This pressure will increase the destruction of PFAS especially in the presence of oxidative reactions such as electrooxidation, photo and electro Fenton, non-Fenton, and Fenton-like actions and bipolar ionized air injection.

[0064] In one example PFAS contaminated water was treated with an example of the above system and method. In the initial sample, no fluoride was measurable. However, during treatment using the above system fluoride levels increased indicating break down of the PFAS and mineralization of the fluorine into fluoride, while the mineralized compounds settled within the vessel, separating from treated water.

[0065] One or more catalysts can be placed or injected into the pressure vessel prior to or during the pressurization of the vessel to increase oxidation or reformation of certain elements and compounds. An electrical current can be applied to the catalyst media within the vessel. The materials as exemplarily described in US 11572297 may be added to the vessel prior to treatment,or may be added to the contaminated water prior to filling the vessel. This can increase the reactivity and effectiveness of the biopolymeric formulations. It may demineralize and release H, 02, Si, Fe, Al, Ca, Mg, and other elements from Biopolymeric chemistry. Relatedly, “spent” materials as exemplarily described in US 11572297 saturated with contaminants may be treated to remove the contaminants therefrom leaving the material for reuse or repurpose.

[0066] In another example of the arrangement and use of the systems described above, a body of water, for example, a lake, pond, lagoon, tank, pool, well, etc. may be treated in two stages by first applying a geopolymer mixture having some or all of bentonite, zeolite, activated carbon, and magnesium oxide to the body of water, for example in the form of a slurry sprayed or injected into the body of water, followed by a similar application of a biopolymer, for example chitosan acetate, promoting adsoiption of contaminants to the geopolymer mixture and coagulation and settling of the geopolymer and adsorbed contaminants. Next, the electrolysis system 100 or 300 is incorporated in-line with a water source and is used to treat relatively contaminant-free water with the above process, resulting in ionized water, this ionized water entrained with hydrogen peroxide and hydroxyls to the body of water. This treatment may interact with the adsorbed contaminants to treat the contaminants in-place at the bottom of the body of water.

[0067] The geopolymer and / or biopolymer media can be applied to the water body and allowed to coagulate and flocculate. The ionized and electro-oxidated water can be created as described above ex-situ or in-situ and then applied to the body of water. The combination of the addition of the geopolymer material and the hydroxyl rich water created by the bipolar ionization and electrooxidation creates Fenton, non-Fenton, and Fenton-like oxidative reactions. These reactions can cause an upwelling effect in the water. This combination can be used to liberate legacy contaminants, PF AS, algae, and microplastics from the benthic layer and lower portions of water bodies. These suspended solids can then further be removed, treated, and / or harvested.

[0068] In still further examples, this treatment may be performed without the initial application of the geopolymer and / or biopolymer material. Low dissolved oxygen and toxins created by cyanobacteria in freshwater or by karenia brevis in salt water can be exemplarily be treated with an example of the disclosed system. Water enriched with ionized air and electrooxidated with the system described above, can be used as an oxidative solvent-free reagent in order to raise dissolved oxygen, stimulate aerobic microorganisms that metabolize excess nutrients that cause eutrophication, while destroying harmful algae and algal toxins. Such an implementation ofthe system could be placed on site for in-situ continuous maintenance, or the ion and electro oxidated water could be sprayed cx-situ onto the surface and / or onto active algae blooms. In related examples, this hydroxyl-rich water may also be used to spray apply onto the ground, injected into the ground, or used in irrigation to accelerate the breakdown of contaminants, stimulate microbial activity, suppress pests, and pathogens, or stimulate plant growth. For example, the treated hydroxyl-rich water may also be applied onto plants / crops to destroy or otherwise inhibit pests and pathogens, treat for diseases, or stimulate plant growth without chemicals. This approach could also potentially be found useful for the breakdown of microplastics present in the pores of crops / plants.

[0069] In another variation of the above disclosure, the system may be used in an in-situ system to treat contaminants in soil. A grid of anodes and cathodes, and ionized air and H2O2 injectors are positioned within the soil of the ground to be treated. The biopolymeric media as exemplarily described in US 11572297 is injected into a liquid stream then applied onto the soil. The anode and cathode network are energized to break down specific contaminants while having a compounding oxidative effect with the bipolar ions, hydrogen, oxygen, and H2O2 enriched water. Ionized air, H2O2, and the electrode system will break down contaminants (PFAS, VOC’s, PCB’s, pesticides, herbicides, hydrocarbons, etc.) in soil. The biopolymeric materials further the sequestration, neutralization, and / or oxidation of contaminants in the soil.

[0070] Citations to a number of references are made herein. The cited references are incorporated by reference herein in their entireties. In the event that there is an inconsistency between a definition of a term in the specification as compared to a definition of the term in a cited reference, the term should be interpreted based on the definition in the specification.

[0071] In the above description, certain terms have been used for brevity, clarity, and understanding. No unnecessary limitations are to be inferred therefrom beyond the requirement of the prior ait because such terms are used for descriptive purposes and are intended to be broadly construed. The different systems and method steps described herein may be used alone or in combination with other systems and methods. It is to be expected that various equivalents, alternatives and modifications are possible within the scope of the appended claims.

[0072] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of theclaims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims

CLAIMSI claim:

1. A water treatment system comprising: a vessel configured to receive water comprising at least one contaminant into an interior of the vessel; a plurality of cathodes arranged within the interior of the vessel; a plurality of anodes arranged within the interior of the vessel at a ratio of two anodes per cathode; a power supply connected to the plurality of cathodes and the plurality of anodes; and a light source, comprising at least one of an infrared (IR) light source, an ultraviolet (UV) light source, and / or a laser light source.

2. The water treatment system of claim 1, further comprising a waveform generator connected between the power supply and the plurality of cathodes and the plurality of anodes, wherein the waveform generator provides electrical energization between the plurality of cathodes and the plurality of anodes at a frequency of at least 15 kilohertz.

3. The water treatment system of claim 1, wherein the light source comprises at least one of an infrared (IR) light source, an ultraviolet (UV) light source, and a laser light source.

4. The water treatment system of claim 3, wherein the laser light source has a wavelength between 435-1400 nm.

5. The water treatment system of claim 3, wherein the UV light source emits light within the UV-C band6. The water treatment system of claim 3, wherein the IR light source emits light between 780 nm and 1060 nm.

7. The water treatment system of claim 1, wherein the plurality of cathodes and the plurality of anodes are arranged in at least two concentric rings within the vessel.

8. The water treatment system of claim 1 , wherein the plurality of cathodes and the plurality of anodes arc arranged in a pattern of repeating groups of anode - cathode - anode.

9. The water treatment system of claim 8, wherein the cathodes of the plurality of cathodes comprise graphite and the anodes of the plurality of anodes comprise titanium.

10. The water treatment system of claim 1, wherein the power supply is inclusively between 24-120 volts and 25-100 amps.

11. The water treatment system of claim 1, further comprising: a gas source configured to supply a gas; and a piping assembly connected to the gas source and configured to release dispersed bubbles of gas into the water comprising at least one contaminant.

12. The water treatment system of claim 11, wherein the gas is air, ionized air, oxygen, ozone, or nitrogen.

13. The water treatment system of claim 12, wherein the gas is ionized air and the gas source comprises an ionizer.

14. The water treatment system of claim 11, wherein the piping assembly extends into the vessel and the dispersed bubbles of gas are released into the water comprising at least one contaminant within the vessel.

15. The water treatment system of claim 12, wherein the vessel is a first vessel and further comprising a second vessel, the second vessel configured to receive the water comprising at least one contaminant into an interior of the second vessel, wherein an outlet of the second vessel is connected to the inlet of the first vessel, and wherein the piping assembly extends into the second vessel and the dispersed bubbles of gas are released into the water comprising at least one contaminant within the second vessel.

16. The water treatment system of any of claim 15, further comprising a gas outlet at the top of the second vessel and a fraction outlet positioned adjacent to the gas outlet.

17. The water treatment system of claim 16, wherein the second vessel comprises a collection bell and the gas outlet and the fraction outlet are within the collection bell.

18. The water treatment system of claim 17, further comprising at least one filter connected to the gas outlet and configured to remove at least one substance from the gas exiting the gas outlet.

19. The water treatment system of claim 18, wherein the at least one filter comprises at least one of the filter media selected from a desiccant, activated carbon, redox alloys, zeolite, metal organic frameworks, covalent organic frameworks, ethylene glycol, and methanol.

20. The water treatment system of claim 19, whereby gas exiting the at least one filter is redirected to at least one of the gas source or the first vessel.

21. The water treatment system of claim 18, further comprising a laser oxidation system comprising a 50 W or greater pulsed fiber laser, wherein a foam fraction of the at least one contaminant in the water in the collection bell is provided under a negative pressure to the laser oxidation system and subjected to the output of the pulsed fiber laser.

22. The water treatment system of claim 21 further comprising a connection between the laser oxidation system and the at least one filter, whereby gas emitted from the laser oxidation of the foam fraction is directed to the at least one filter.

23. The water treatment system of claim 15, further comprising a source of biopolymer and / or geopolymer, wherein the source of biopolymer and / or geopolymer provides biopolymer and / or geopolymer to the water comprising at least one contaminant as it flows from the second vessel to the first vessel.

24. The water treatment system of claim 23, further comprising a third vessel fluidly connected between the second vessel and the first vessel, wherein the source of biopolymer and / or geopolymer provides the biopolymer and / or geopolymer to the third vessel to form a homogeneous mixture with the water comprising the at least one contaminant, and wherein at least some of the at least one contaminant adsorbs onto the biopolymer and / or geopolymer.

25. The water treatment system of claim 1, further comprising a collection funnel at a bottom of the vessel.

26. The water treatment system of claim 1, further comprising an ultrasound emitter configured to emit sound waves into the vessel.

27. The water treatment system claim 1, wherein the water received in the vessel further comprises an additive of a geopolymer and / or a cationic biopolymer.

28. A method of water treatment using the water treatment system of claim 1, the method comprising: receiving water comprising at least one contaminant within the vessel; providing electrical energization to the plurality of cathodes and the plurality of anodes; and energizing the light source to expose the water comprising at least one contaminant to at least one wavelength of light energy emitted from the light source.

29. The method of water treatment of claim 28, wherein the light source is an infrared (IR) light source, and further comprising an ultraviolet (UV) light source and a laser light source, the method comprising: emitting light energy between 780nm-1060nm from the IR light source into the water comprising at least one contaminant; emitting light energy between 100nm-280nm from the UV light source into the water comprising at least one contaminant; andemitting light energy between 435-590nm from the laser light source into the water comprising at least one contaminant.

30. The method of water treatment of either claim 28, further comprising: providing diffused bubbles of gas to the vessel and venting the gas from the vessel.

31. The method of any of claims 28, wherein at least two of the steps are performed concurrently.

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