Improved apparatus for electrochemical treatment of water and methods of use

Abstract

Apparatus and methods for removal and degradation of at least one contaminant from a fluid stream are provided, the apparatus having at least one electrochemical cell operably integrated with at least at least one active retention unit (ARU), the electrochemical cell operative to generate at least one oxidizing agent for contacting and directly degrading the at least one contaminants adsorbed to the ARU, and to generate a high oxidation state to further degrade the adsorbed contaminant and restore the ARU to an original oxidative state.

Description

IMPROVED APPARATUS FOR ELECTROCHEMICAL TREATMENT OF WATER AND METHODS OF USECROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 574,526 filed April 4, 2024, entitled “Improved Apparatus for Electrochemical Treatment of Water and Methods of Use”, which is specifically incorporated by reference herein for all that it discloses or teaches.FIELD

[0002] Embodiments herein are generally related to improved systems and methods for the treatment of fluids, such as water, wastewater, and greywater. Specifically, embodiments are generally related to the optimization of electrochemical treatment of the fluids to enhance removal of, inter alia, dissolved organic matters (DOM).BACKGROUND

[0003] The increasing presence of organic pollutants such as pesticides, dyes, pharmaceutical compounds, and biofilms in water ecosystems is a growing environmental concern, particularly as industrial activities expand. The textile industry alone accounts for 4% of global freshwater consumption and contributes to 20% of industrial wastewater pollution, releasing large volumes of synthetic dyes and chemical contaminants into water systems. With rising water costs, escalating water stress, and increasing regulatory pressure, textile manufacturers are seeking innovative solutions to reduce water pollution and improve sustainability.

[0004] However, current wastewater treatment plants (WWTPs) and ship-based greywater treatment systems are largely ineffective in removing these persistentpollutants from effluent, leading to widespread environmental contamination. These conventional treatment technologies require complex infrastructure, generate both solid and liquid waste, and cannot be implemented as decentralized add-on units, limiting their adaptability for industries seeking efficient, on-site solutions. Addressing this challenge requires advanced water treatment technologies capable of effectively eliminating organic pollutants from industrial wastewater.

[0005] There is a clear need for improved systems and methods for effectively removing organic pollutants from water, including wastewater and / or greywater.

[0006] Various attempts have been made to eliminate organic pollutants from wastewater. Some attempts have focused on physical separation of the pollutants from the wastewater, such as through adsorption and membrane separation techniques, while other attempts have focused on oxidative degradation of the pollutants, such as through advanced oxidation techniques.

[0007] More specifically, some membrane separation techniques can provide the selective entrapment of organic compounds from wastewater using physical retention methods including settling treatments, biofilters, bioreactors, and / or biologically active filters. For example, some membrane separation techniques comprise physical filtration methods characterized by their ability to sieve compounds of different sizes and characteristics.

[0008] Known membrane separation techniques however, can have limited efficiencies and are highly dependent upon the size, shape, charge, and / or type of compound, as well as whether the techniques are used alone or in combination with other treatments. Known membrane separation techniques also often require themembrane to have active role in separate the compounds (e.g., the membrane itself serves to chemically bind with the compounds), resulting in compounds only being retained within the membrane for a short time and decreasing the overall lifespan of the membrane (e.g., membrane covered with catalyst has a shorter lifetime). Known membrane separation techniques can also suffer from surface fouling, causing the problems of membrane permeation flux and retention drop, and requiring efficient, stable cleaning procedures. Moreover, known membrane separation techniques also typically only serve to capture the pollutants from the wastewater, necessitating additional processing treatments to degrade the captured fragments.

[0009] Advanced oxidation processes, such as electrochemical oxidation, can provide rapid and non-selective oxidation of organic compounds in wastewater. Within the field of electrochemical treatment of wastewater, there are two primary approaches to the oxidation of contaminants, namely, the direct electrochemical oxidation of compounds directly on the anode surface, and the indirect electrochemical oxidation of compounds through the in-situ generation of chemically oxidizing species (such as hydroxyl, chlorine, oxygen, or perchlorate radicals, or compounds such as hypochlorite, ozone, or hydrogen peroxide). These chemically oxidizing species are generated directly on the anode surface and subsequently oxidize contaminants in bulk solution (i.e. , within the wastewater).

[0010] A variety of electrochemical cell configurations include flow-through parallel plates, divided chambers, packed bed electrodes, stacked discs, concentric cylinders, moving bed electrodes and filter-press have been developed for both direct and indirect electrochemical treatment of fluids. However, common to all of theseelectrochemical cell configurations is poor operational efficiency and performance leading to high energy consumption and / or low contaminant removal rates. Moreover, such electrochemical cell configurations can also suffer from a relatively short lifetime of the electrodes and the increased costs associated with needing to replace the consumed electrodes, particularly where sacrificial anodes are used.

[0011] For example, due to the very low ionic conductivity of wastewater, known systems that use wastewater as the electrolyte require the addition of significant concentrations of supporting chemical electrolytes to improve cell efficiency and obtain reasonable cell voltages. This requirement can lead to the need for added anolytes and / or catholytes with base concentrations and pHs that are non-compliant with contaminant and pH discharge limits, adding cost to the treatment for both the disposal of the treated wastewater and handling of the added electrolytes. Large electrode gaps and low surface area electrodes can also contribute to efficiency losses and low contaminant removal rates. For example, slow mass transport in the pores of porous beds and non-optimized catalyst materials with poor reaction kinetics requiring high electrode overpotentials also contribute to lower performance efficiency and losses. Such operating conditions can lead to the need for large, complex reactors. Known oxidative electrochemical systems can also require large amounts of additionally added chemicals and / or feed oxygen and provide secondary pollution that creates additional costs and are often hazardous to the environment.

[0012] Many attempts have been made to increase the performance of electrochemical cells for wastewater treatment. However, to date, there remains a need for an improved apparatus and methods of use for removing pollutants fromwastewater, such apparatus operative to enhance the removal of, inter alia, dissolved organic matter from the wastewater. In particular, the textile industry requires more effective solutions for eliminating pollutants such as dyes, surfactants, per- and polyfluoroalkyl substances (PFAS), and softeners, etc. which are commonly found in its wastewater effluent. An ideal solution would be one that can be easily integrated into existing processes with minimal infrastructure requirements and without generating additional solid or liquid waste.SUMMARY

[0013] According to embodiments, an apparatus and methods of use for removal and degradation of at least one contaminant from a fluid stream are provided, the apparatus comprising at least one electrochemical cell, the cell having an inlet end for receiving the fluid stream having the at least one contaminant, at least one electrode for generating at least one oxidizing agent, at least one active retention unit (ARU), in fluid communication with the at least one electrode, the ARU for adsorbing the at least one contaminant from the fluid stream, and at least one outlet end for discharging the fluid stream. In some embodiments, the at least one oxidizing agent from the at least one electrode may be supplied to the at least one ARU to directly degrade the at least one contaminant adsorbed to the ARU and to generate a high oxidation state to degrade the adsorbed contaminant and further to restore the ARU to an original oxidative state.

[0014] In some embodiments, the at least one ARU comprises at least one active material substance for adsorbing the at least one contaminant. In some embodiments,the at least one active material substance may be selected from iron (III) oxide, potassium manganate, or the like.

[0015] In some embodiments, the at least one oxidizing agent comprises hydroxyl radicals.

[0016] In some embodiments, at least a portion of the contaminants may be dissolved organic matter.

[0017] In some embodiments, the apparatus may comprise at least one anode and at least one cathode.

[0018] In some embodiments, the fluid stream may comprise blackwater, greywater, wastewater, or water.

[0019] In some embodiments, at least a portion of the discharged fluid stream from the outlet end may be recirculated or redirected back to the inlet end of the electrochemical cell.

[0020] According to embodiments, methods of removing and degrading at least one contaminant from a fluid stream are provided, the methods comprising providing at least a portion of the fluid stream to an apparatus having an electrochemical cell in fluid communication with at least one active retention unit (ARU), the ARU for adsorbing the at least one contaminant from the fluid stream, allowing the at least one contaminant to adsorb to the at least one ARU, operating the electrochemical cell to generate at least one oxidizing agent, supplying the at least one oxidizing agent to the at least one ARU to directly degrade the at least one contaminant adsorbed to the ARU and generate a high oxidation state to further degrade the adsorbed contaminantand to restore the ARU to an original oxidation state, and discharging at least a portion of the fluid stream to the outlet as an output fluid stream.

[0021] In some embodiments, the AFU may comprise at least one active material substance for adsorbing the at least one contaminant. In some embodiments, the active material substrate may be selected from iron (III) oxide, potassium manganate, or the like.

[0022] In some embodiments, the at least one oxidizing agents may be hydroxyl radicals. In some embodiments, the at least one oxidizing agents may restore the at least one ARU by regenerating the active material substance.

[0023] In some embodiments, the at least one contaminant comprises may be dissolved organic matter.

[0024] In some embodiments, the input fluid stream may be introduced to the apparatus continuously, intermittently, or a combination thereof. In some embodiments, the input fluid stream may be introduced to the electrochemical cell, to the at least one AFU, or a combination thereof.

[0025] In some embodiments, operating the electrochemical cell may comprise operating at least one electrode. In some embodiments, operating the at least one electrode may comprise operating at least one anode, at least one cathode, or a combination thereof.

[0026] In some embodiments, the method comprises reintroducing at least a portion of the output fluid stream to the apparatus. In some embodiments, the fluid stream may comprise greywater, wastewater, or water.BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Embodiments of the present disclosure will now be described, by way of example only, with reference to the attached Figures.

[0028] Figure 1 (PRIOR ART) shows a graphical representation of an electrochemical cell for fluid treatment, the cell being referred to only for the purposes of explanation of the present methods, with fluid flowing through the cell (arrows), for example such fluid flowing through a plurality of apertures formed within a physical retention unit of the cell, according to embodiments;

[0029] Figure 2 shows an example representation of the presently improved apparatus providing an active filtration unit, according to embodiments;

[0030] Figure 3A shows an example representation of a first embodiment of the presently improved apparatus shown in FIG. 2, according to embodiments;

[0031] Figure 3B shows an example representation of a second embodiment of the presently improved apparatus shown in FIG. 2, according to embodiments;

[0032] Figure 4 shows an example representation of a third embodiment of the presently improved apparatus shown in FIG. 2, according to embodiments; and

[0033] Figure 5 provides the results generated by the use of the presently improved apparatus, according to embodiments.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] According to embodiments, an improved apparatus and methods of use are provided for the removal and degradation of at least one contaminant from a fluid stream, including dissolved organic matter from water, greywater, wastewater, and the like. In some embodiments, the presently improved apparatus and methods of usemay provide enhanced removal and degradation of the at least one contaminant by, without limitation, combining adsorption and electrochemical oxidation processes.

[0035] According to embodiments, the presently improved apparatus and methods of use may first provide an active material substrate (sorbent) serving as a medium to which the contaminants are adsorbed before and during degradation, and second an electrooxidation process, where oxidizing agents (e.g., hydroxyl radicals) are generated serving to degrade the trapped (adsorbed) contaminants. As such, advantageously, the oxidizing agents generated by the electrooxidation process serve to increase the oxidation state of the sorbent, allowing the sorbent to directly contribute to the breakdown of contaminants. In this manner, the presently improved apparatus and methods may be configured to enhance degradation of contaminants by combining the synergistic effects of both adsorption and electrochemical oxidation processes.

[0036] Moreover, in some embodiments, the presently improved apparatus and methods of use may be configured for electrooxidation (i.e. , the generation of oxidizing agents) such that, with each electrooxidation cycle, the active sorbent may be restored by degrading the trapped contaminant and then recovering its original oxidation state, thereby ensuring its adsorption and electrochemical activity is maintained In some embodiments, the material may be ready for reuse in subsequent cycles of fluid treatment, improving the long-term efficiency, residence time, and sustainability the apparatus. More specifically, it is an advantage of the presently improved system that the generation of oxidizing agents may serve to both degrade the contaminants adsorbed by the material substrate and to create a higher oxidation state, restoringthe active substrate and providing a self-regenerating system operative to increase the overall efficacy of the system.

[0037] By way of background, having regard to FIG. 1 (PRIOR ART) solely for the purposes of explanation herein, electrochemical cells 2 are known to be used for removing and degrading contaminants from fluid streams, such as the cell described in International Patent Application No. PCT / CA2022 / 050375, incorporated herein in its entirety by reference. Such known electrochemical cells can comprise a physical retention unit (PRU) 4 formed from a retention material 6 for capturing the contaminants, and at least one electrode 8 (anode 3; cathode 5) operably connected to the PRU 4 for degrading the captured contaminants. The electrodes, including the at least one anode 3 and at least one cathode 5 may be positioned within the PRU 4 (although other configurations of electrochemical cells are contemplated), and the fluid being treated is introduced to the cell via an input fluid stream 12. The electrochemical cell is then operated to generate at least one oxidizing agent for degrading the captured contaminants, following which the treated fluid stream 14 is discharged from the cell as at least one output fluid stream 18. In some cases, some or all of the output fluid stream 18 may be recycled and recirculated back through the electrochemical cell (via stream 16), enabling a regenerative oxidative process, providing a selfcleaning system without the use of chemicals or the generation of added waste.

[0038] The presently improved apparatus and methods of use will now be described having regard to FIGS. 2 - 5.

[0039] Certain terminology may be used in the present description and is intended to be interpreted according to the definitions provided below.

[0040] Herein, the term ‘active material substance’ ‘activate material substance’, ‘activated material substrate’, ‘sorbent’, or ‘sorbent material’ are used interchangeably to mean any material capable of increasing its oxidation state and capturing contaminant molecules (adsorbate) onto the surface by intermolecular interaction including, without limitation, iron oxide, iron (III) oxide (e.g., hematite Fe2Os, magnetite FesCM, goethite FeOOH), potassium manganate (KMnCM), or other suitable materials having high surface charge variability and affinity for organic contaminants.

[0041] Herein, the terms ‘contaminant(s)’ and / or ‘pollutant(s)’ are used interchangeably to mean any molecule, cell, or particulate to be removed from a fluid stream including, without limitation, dissolved solid compounds including organic compounds such as, pesticides, fertilizers, surfactants, pfas, textile and / or other dyes (e.g., green and black dyes, tartrazine, or methylene blue), pharmaceuticals, bacteria, viruses, and / or biofilms. In some embodiments, at least a portion of the fluid stream may comprise blackwater, greywater and / or wastewater. In other embodiments, at least a portion of the fluid stream may comprise water for water purification.

[0042] Herein, the terms ‘dissolved organic matter’, or ‘DOM’ are used to mean organic compounds naturally present in water or those generated through human activities and / or industrial activities.

[0043] Herein, the terms "blackwater', ‘greywater’, or ‘wastewater’ are used interchangeably to mean urban and domestic wastewater commonly generated in households, office or industrial buildings, ships, aircraft, and vehicles from sinks, showers, baths, and washing machines or dishwashers (i.e., all urban and domestic fluid streams excluding the wastewater from toilets, or that contain fecal matter).

[0044] Herein, the terms ‘oxidizing or oxidative radicals’, ‘oxidizing or oxidative species’, ‘oxidizing or oxidative agents’, and products of at least one ‘oxidative reaction’ means any potent oxidant species or substance operative as an oxidizer, i.e. , having the ability to oxidize another substance.

[0045] Each term used and defined herein is for explanatory purposes only and in no way is intended to limit the scope of the technology.

[0046] According to embodiments, having regard to FIG. 2, the presently improved apparatus 10 for the removal and degradation of at least one contaminant may comprise at least one electrochemical cell 10 having an inlet end configured to receive, continuously, intermittently, or a combination thereof, a fluid input stream 12 and an outlet end configured to discharge a fluid output stream 14. In some embodiments, the fluid input stream or ‘influent’ 12 contains at least one contaminant to be removed from the stream and, once removed, the fluid stream forms the treated output stream 14 discharged from the cell 10.

[0047] According embodiments, the presently improved apparatus 10 may comprise at least one electrode 20 for generating at least one oxidizing agent, such oxidizing agent serving as a highly reactive species capable of breaking down contaminants in the fluid stream 12 being treated into smaller, less harmful molecules. In some embodiments, the at least one oxidizing agents may comprise hydroxyl radicals (*OH).

[0048] In some embodiments, the at least one electrode 20 may comprise at least one anode 22 (oxidation site) and at least one cathode 24 (reduction site), for generating the oxidizing agents (via oxidation). As would be appreciated, operation of the at least one electrode 20 may comprise applying a voltage across the at least one anode 22and cathode 24, generating an electron flow through a conductive medium, and facilitating an electrochemical reaction at the anode 22 and / or cathode 24. As will be described, the electrochemical cell 20 may be operably connected to at least one active retention unit (ARU). In some embodiments, the electrochemical cell 20 may be in fluid communication with the ARU, such that oxidizing agents generated by cell 20 are supplied or introduced to the ARU.

[0049] According to embodiments, the presently improved apparatus 10 may comprise at least one active retention unit (ARU) 30. In some embodiments, the at least one ARU 30 may serve as a material substrate for capturing (actively filtering) the at least one contaminant. In some embodiments, without limitation, the at least one contaminant may be retained by the material substrate of the ARU 30 via adsorption processes, whereby contaminants (adsorbate) accumulate on the surface of the substrate (sorbent).

[0050] In some embodiments, having regard to FIGS. 2 - 4, the at least one ARU 30 may comprise at least one active retention material or substance 31 for receiving or capturing (i.e. , adsorbing) the at least one contaminant(s). In some embodiments, the active material 31 may comprise at least one specialized adsorption column filled with a high-oxidation state (HOS) adsorbent material that, without limitation, may possess unique adsorption properties, facilitating the interactions and binding of the at least one contaminant. In some embodiments, the active material 31 may comprise an HOS adsorbent material configured to bind and degrade dissolved organic matter within the fluid stream 12. Without being limited by theory, removal of dissolved organic materials from fluid stream 12 introduced into electrochemical cell 20 may serve toenhance the reaction kinetics of the oxidative degradation of radicals within the fluid, optimizing the efficiency of the system.

[0051] According to embodiments, as above and having regard to FIGS. 2 - 5, the at least one ARU 30 may be operably integrated with and connected to the at least one electrode 20, such that oxidizing agents generated by electrode 20 may be introduced to, and contacted with, some or all of activate material 31 of ARU 30.

[0052] In some embodiments, the at least one ARU 30 may be in fluid communication with the at least one electrode 20, such that oxidizing agents 21 (FIG. 4) generated by electrode(s) 20 may be contacted with activate material 31 of ARU 30 (and specifically contaminants adsorbed thereon). In this manner, oxidizing agents 21 generated by electrode(s) 20 may serve to both degrade contaminants adsorbed on ARU 30 to generate a higher oxidation state, to degrade the contaminant, and to restore the active material 31 to its original oxidation state.

[0053] In some embodiments, without limitation, oxidizing agents 21 generated by electrode(s) 20 may be introduced to ARU 30 via input fluid stream 12, or in any other manner suitable in the art. For example, in some embodiments, at least a portion of fluid stream 12 may pass through the at least one electrode 20 before the at least one ARU 30 (FIG. 3A), through the at least one ARU 30 before the at least one electrode 20 (FIG. 3B), through both simultaneously, where the at least one electrode 20 may be positioned within the at least one ARU 30 (FIG. 4), or any combination thereof. It is contemplated that the presently improved apparatus 10 may comprise a plurality of ARUs (e.g., 30a, 30b; FIGS. 3A - 3B), as desired. In some embodiments, the presentlyimproved apparatus 10 may be configured to optimize space, decreasing the overall footprint of apparatus 10.

[0054] In some embodiments, as above, the presently improved systems and methods of use may be configured such that at least a portion of the treated output fluid stream, or ‘effluent’ 14, free of contaminants (and oxidizing agents) may pass from cell 20.

[0055] In some systems, having regard to FIGS. 2, 3A and 3B, at least a first portion 16 of the output stream 14 may be recycled and recirculated or reintroduced back through the at least one electrochemical cell 20, and at least a second portion 18 of the output stream 14 may be discharged as being safe for further treatment, storage, or discard. In some embodiments, the first recirculated portion 16 of the output fluid stream 14 may be combined with input fluid stream 12. Advantageously, recirculation and reuse of at least a portion 16 of the output stream 14 enables a regenerative oxidative process, providing a self-cleaning system without the use of chemicals or the generation of added waste.

[0056] In some embodiments, preemptively passing fluid input stream 12 through at least one ARU 30 prior to electrooxidation may serve to reduce the fraction of the input fluid stream 12 retained for recirculation. For example, in some embodiments, a controlled fraction (e.g., approximately 10% or less VA / ) of the treated output fluid stream 14 may be continuously redirected back into an integrated electrochemical cell 20, where electrochemical reactions generate potent oxidants. Such oxidants produced within cell 20 may be recirculated back to the active ARU 30 (i.e., for contacting the adsorption column of HOS materials therein), ensuring that oxidants come into contact with the adsorbed dissolved organic matter.

[0057] In this regard, the presently improved ‘dual-oxidation’ systems and methods of use employ two distinct mechanisms for the oxidation of dissolved organic matter, namely, electrochemical oxidation, wherein potent oxidizing agents generated within the electrochemical cell 20 actively participate in the oxidation process, contributing to the breakdown of contaminants (e.g., dissolved organic materials, DOM), and HOS material oxidation, wherein the active HOS material, which has undergone an elevated oxidation state due to its interaction with the potent oxidizing agents, also promotes enhanced oxidation of the contaminants (e.g., dissolved organic materials).

[0058] According to embodiments, the presently improved apparatus and methods will now be described having regard to the following examples.

[0059] EXAMPLES

[0060] The following examples are provided for explanatory purposes only.

[0061] Example 1 - the following example shows the use of the presently improved apparatus 10 for the removal of dissolved organic matter (DOM) from a fluid stream, the fluid stream comprising wastewater. The example demonstrates the combined use of an ARU 30 having a high oxidation state adsorption material operably integrated with an electrochemical cell 20 for generating oxidizing agents 21 , thereby enhancing DOM removal. Without limitation, the presently improved apparatus 10 and methods of use serve as a synergistic approach to the treatment of a fluid stream containing at least one contaminant (e.g., DOM), increasing residency time and rate of degradation (e.g., reaction rate) of the contaminant.

[0062] Table 1 - Adsorption. The following table provides the results of methylene blue (MB, [0.0001 M]) sorption tests using iron oxide.

[0063] A first example of organic pollutants degradation using electrooxidation occurred over 1.5 hours plus electrolyte (1 g / L Na2SO4), at a current of 1A and initial voltage of 10V, achieving a final MB concentration of 3.12 E-07M.

[0064] A second example of organic pollutants degradation of sorbed dye over iron using electrooxidation (having activate ARU, 9.97g Fe2O3), occurred over 1.5 hours plus electrolyte (1 g / L Na2SO4), at a current of 1A and initial voltage of 10V, achieving a final MB concentration of 0 mg / L and 0 mg / L chemical oxygen demand (COD).

[0065] Example 2 - the following example shows the use of the presently improved apparatus 10 for the removal of conventional dyes from a fluid stream, the fluid stream comprising water.

[0066] Table 1 - Contaminants. The following table provides the degradation results of various contaminants using iron oxide.

[0067] The example demonstrates the combined use of an ARU 30 having a high oxidation state adsorption material operable integrated with an electrochemical cell 20for generating oxidizing agents 21 , thereby enhancing contaminant removal. In some embodiments, the present example comprised providing at least a portion of a fluid stream to the at least one ARU 30, the ARU 30 comprising an active material substrate 31 (e.g., at least one column filled with iron oxide), and allowing the contaminants to adsorb to the active material substrate 31. In some embodiments, the present example further comprised operating the electrochemical cell 20 to generate at least one oxidizing agent 21 and supplying the at least one agent(s) 21 to the at least one ARU 30. In some embodiments, the methods provided in the present example may be repeated multiple times, for example, at least three times (i.e. , wherein fluid stream 12 is cycled through the at least one ARU 30 (sorption) and electrochemical cell 20 (EOX) at least three times).

[0068] In some embodiments, the results of the present example were determined by measuring the chemical oxygen demand (COD) of the at least one contaminant. It should be appreciated that COD provides an indirect measure of contaminants, i.e., providing organic contamination to evaluate degradation of organic compounds.

[0069] Table 2 - Degradation. The following table provides the degradation results of various contaminants using iron oxide over three cycles through the presently improved apparatus 10.

[0070] In some embodiments, having regard to FIG. 5, the example demonstrates the use of the presently improved apparatus 10 for the effective degeneration of at least one contaminant from a fluid stream and the effective regeneration of the activate material substrate 31. Without limitation, the regeneration process involved electroxidation, which degraded the contaminants (dyes) and allowed for their subsequent re-absorption into the material. The efficiency of dye retention after regeneration was maintained, ensuring the active material substrate 31 demonstrated continued functionality and effectiveness.

[0071] Without limitation, this Example 2 demonstrates the efficacy of the at least one ARU 30 in removing organic contaminants from a fluid stream through the synergistic combination of sorption and electrooxidation processes. The natural iron oxide powder used as the sorbent material 31 effectively adsorbed the contaminants, and the subsequent electrooxidation process served to both degrade the contaminants and regenerated the sorbent material 31 . The high degree of contaminant degradation and the reusability of the sorbent material 31 highlight the methods of use of the presently improved apparatus 10.

[0072] Although a few embodiments have been shown and described, it will be appreciated by those skilled in the art that various changes and modifications can be made to these embodiments without changing or departing from their scope, intent or functionality. The terms and expressions used in the preceding specification have been used herein as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding equivalents of the features shown and the described portions thereof.

Claims

WE CLAIM:1 ) An apparatus for removal and degradation of at least one contaminant from a fluid stream, the apparatus comprising: at least one electrochemical cell, the cell having an inlet end for receiving the fluid stream having the at least one contaminant, at least one electrode for generating at least one oxidizing agent, at least one active retention unit (ARU), in fluid communication with the at least one electrode, the ARU for adsorbing the at least one contaminant from the fluid stream, and at least one outlet end for discharging the fluid stream, wherein the at least one oxidizing agent from the at least one electrode contacts the at least one ARU to directly degrade the at least one contaminant adsorbed to the ARU and to generate a high oxidation state to degrade the adsorbed contaminant and restore the ARU to an original oxidative state.2) The apparatus of claim 1 , wherein the at least one ARU comprises at least one active material substance for adsorbing the at least one contaminant.3) The apparatus of claim 2, wherein the at least one active material substance is iron (III) oxide or potassium manganate.4) The apparatus of claim 1 , wherein the at least one oxidizing agent comprises hydroxyl radicals.5) The apparatus of claim 1 , wherein at least a portion of the contaminants are dissolved organic matter.6) The apparatus of claim 1 , wherein the apparatus comprises at least one anode and at least one cathode.7) The apparatus of claim 1 , wherein the fluid stream comprises blackwater, greywater, wastewater, or water.8) The apparatus of claim 1 , wherein at least a portion of the discharged fluid stream from the outlet end is recirculated to the inlet end of the electrochemical cell.9) A method of removing and degrading at least one contaminant from a fluid stream, the method comprising: providing at least a portion of the fluid stream to an apparatus having an electrochemical cell in fluid communication with at least one active retention unit (ARU), the ARU for adsorbing the at least one contaminant from the fluid stream, allowing the at least one contaminant to adsorb to the at least one ARU, operating the electrochemical cell to generate at least one oxidizing agent, supplying the at least one oxidizing agent to the at least one ARU to directly degrade the at least one contaminant adsorbed to the ARU and generate a high oxidation state to further degrade the adsorbed contaminant and to restore the ARU to an original oxidation state, anddischarging at least a portion of the fluid stream to the outlet as an output fluid stream.10)The method of claim 9, wherein the AFU comprises at least one active material substance for adsorbing the at least one contaminant.11 )The method of claim 11 , wherein the active material substrate comprises iron (III) oxide or potassium manganate.12) The method of claim 9, wherein the at least one oxidizing agents are hydroxyl radicals.13)The method of claim 9, wherein the at least one oxidizing agents restore the at least one ARU by regenerating the active material substance.14)The method of claim 9, wherein the at least one contaminant comprises dissolved organic matter.15)The method of claim 9, wherein the input fluid stream is introduced to the apparatus continuously, intermittently, or a combination thereof.16)The method of claims 9, wherein the input fluid stream may be introduced to the electrochemical cell, to the at least one AFU, or a combination thereof.17)The method of claim 9, wherein operating the electrochemical cell comprises operating at least one electrode.18)The method of claim 17, wherein operating the at least one electrode comprises operating at least one anode, at least one cathode, or a combination thereof.19)The method of claim 9, wherein the method comprises reintroducing at least a portion of the output fluid stream to the apparatus.20)The method of claim 9, wherein the fluid stream comprises blackwater, greywater, wastewater, or water.

Images