US20090152123A1 - Methods and Apparatus for Generating Oxidizing Agents - Google Patents

Methods and Apparatus for Generating Oxidizing Agents Download PDF

Info

Publication number
US20090152123A1
US20090152123A1 US11/994,967 US99496706A US2009152123A1 US 20090152123 A1 US20090152123 A1 US 20090152123A1 US 99496706 A US99496706 A US 99496706A US 2009152123 A1 US2009152123 A1 US 2009152123A1
Authority
US
United States
Prior art keywords
anode
carbon felt
aqueous solution
cell
typically
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/994,967
Other languages
English (en)
Inventor
Dean Butler
Robert Lewis Clarke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
APPLIED INTELLECTUAL CAPITAL Ltd
Original Assignee
Applied Intellectual Capital
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Applied Intellectual Capital filed Critical Applied Intellectual Capital
Priority to US11/994,967 priority Critical patent/US20090152123A1/en
Assigned to APPLIED INTELLECTUAL CAPITAL reassignment APPLIED INTELLECTUAL CAPITAL ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BUTLER, DEAN, CLARKE, ROBERT LEWIS
Assigned to AIC NEVADA INC. reassignment AIC NEVADA INC. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: APPLIED INTELLECTUAL CAPITAL
Assigned to APPLIED INTELLECTUAL CAPITAL LIMITED reassignment APPLIED INTELLECTUAL CAPITAL LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AIC NEVADA, INC.
Publication of US20090152123A1 publication Critical patent/US20090152123A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C02F2103/325—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of wine products
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4611—Fluid flow
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • C02F2201/46185—Recycling the cathodic or anodic feed

Definitions

  • the field of the invention is devices and methods for electrochemical generation of oxidizing species, especially as they relate to anodic in situ generation of such species in a fluid.
  • Oxidative species including ozone, hypochlorite, hydrogen peroxide, persulfate, chlorine dioxide, and hydroxyl radicals are frequently used to sterilize water and destroy toxic organic compounds.
  • Oxidative species some exhibit sufficient chemical stability in water to keep the water sterile over relatively long periods, while other oxidative species (e.g., ozone) have relatively short half lives in water, which potentially allows re-infection of previously sterilized water.
  • hypochlorite (OCl ⁇ ) is typically prepared by adding chlorine gas or sodium hypochlorite solutions to water. Hypochlorite is relatively stable, non toxic to humans, and thought to oxidize bacterial cell membranes. Hypochlorite is also known to bleach numerous colored substances, typically by oxidation of aromatic ring structures in the colored substance. Unfortunately, hypochlorite is also known to react with naturally occurring organic materials, including fulvic and humic acids (e.g., present in soil and sediments in lakes, rivers, and ground water) to form chloromethanes and other toxic byproducts.
  • fulvic and humic acids e.g., present in soil and sediments in lakes, rivers, and ground water
  • hypochlorite produces a relatively bad taste in the treated water.
  • ozone may be employed as a sterilization agent.
  • Ozone is chemically more aggressive as a sterilizing agent, but is often more expensive and has a relatively short half life in water. Therefore, ozone sterilization typically requires in situ production at the point of use.
  • hydrogen peroxide may be employed as a sterilizing agent via photolytic cleavage of the H 2 O 2 to generate the OH radical as active species. While the hydroxyl radical is an even stronger oxidizing agent as compared to ozone, the hydroxyl radical also has the shortest half life in water.
  • photolytic hydroxyl radical generation is often limited by turbidity or other compounds that absorb and/or scatter incident light.
  • Electrosynthesis Corp. developed a device based on precious metal coated niobium electrodes which was installed in a water stream.
  • Diamond coatings are characterized as having very high oxygen overpotentials, which is thought to be a prerequisite for generating hydroxyl radicals and/or oxidizing organic materials at high efficiency.
  • Magneli phase titanium suboxide electrodes have been employed to create a device that was effective as a sterilizing device in contaminated waters (Magneli phase titanium oxide is characterized by its high oxygen overvoltage).
  • Electrode materials are either often relatively expensive, difficult to replace by an inexperienced user, and/or typically require relatively large amounts of energy to provide efficient sterilization/decontamination.
  • a method of treating an aqueous solution in which an electrolytic cell is provide having an anode in an anode compartment, a cathode in a cathode compartment, and a diaphragm separating the anode compartment from the cathode compartment.
  • the anode comprises a carbon felt that is conductively coupled to an electrical connector such that a flow path is formed to allow flow of the aqueous solution through the carbon felt.
  • the aqueous solution is moved through the anode compartment such that substantially the entire solution passes through the carbon felt from one side to another side, and in yet another step, the electrolytic cell is operated at a current density effective to generate oxidative species in an amount sufficient to oxidize a contaminant in the aqueous solution.
  • the contaminant in the aqueous solution may vary from source to source, and suitable contaminants include bacteria, spores, viruses, eukaryotic cells and fragments of thereof, optionally halogenated aromatic organic compounds, and dyes. Where desirable, it is also contemplated to recycle at least part of the aqueous solution back to the anode compartment after the solution has passed through the carbon felt.
  • FIG. 1 is a schematic view of one exemplary device according to the inventive subject matter.
  • FIG. 2 is a schematic view of another exemplary device according to the inventive subject matter.
  • high-surface area carbon felts provide for highly effective in situ flow-through anodes for sterilization and chemical decontamination, especially when operated in substantially neutral (pH of between about 5.5 and 8.5) aqueous streams. Most typically, sterilization and chemical decontamination is achieved by production of oxidizing species rather than by direct anodic oxidation of the contaminants. Remarkably, the high-surface area carbon felts remained undegraded, even at current densities ordinarily expected to destroy the carbon felt anode to carbon dioxide.
  • the carbon anode is substantially completely covered by a protective mixed crystal coating consisting essentially of ruthenium oxide and titanium oxide (Reger et al. describe and depict oxidative destruction of uncoated materials as comparative examples). Still other carbonaceous electrodes are described in, for example, U.S. Pat. Nos.
  • the anode in all known carbonaceous anodes, the anode is only used as a ‘static electrode’ that is in contact with the anolyte.
  • the electrolyte is in substantially non-moving contact with the internal surfaces of the porous or otherwise high-surface anode and thus subject to oxidation of locally generated oxidative species, especially where the anode is operated at conditions that promote formation of such oxidative species.
  • the inventors contemplate that by continuously passing the anolyte through the entire volume (including the internal surfaces) of the anode, oxidative damage from oxidative species to the anode is avoided as the oxidative species either react with a passing contaminant in the electrolyte, are removed from direct contact with the anode by the moving anolyte, and/or otherwise decay due to their chemical instability.
  • the oxidizing species may be ‘washed off’ the anode before reaching residence time and quantities sufficient to damage the anode.
  • carbon felt refers to a textile material that predominantly comprises randomly oriented and intertwined carbon fibers, which are typically fabricated by carbonization of organic felts (see e.g., IUPAC Compendium of Chemical Terminology 2nd Edition (1997)). Most typically, organic textile fibrous felts are subjected to pyrolysis at a temperature of at least 1200° K, more typically 1400° K, and most typically 1600° K in an inert atmosphere, resulting in a carbon content of the residue 90 wt %, more typically 95 wt %, and most typically 99 wt %.
  • contemplated carbon felts will have a surface area of at least about 0.01-100 m 2 /g, and more typically 0.1-5 m 2 /g, most typically 0.3-3 m 2 /g, and where the carbon felt is activated, will have a surface area (BET) of more than 100-500 m 2 /g, more typically at least about 500-800 m 2 /g, even more typically at least about 800-1200 m 2 /g, and most typically at least about 1200-1500 m 2 /g, or even more.
  • the carbon felt may be graphitic, amorphous, have partial diamond structures (added or formed by carbonization), or a mixture thereof.
  • reticulated or vitreous (glassy) carbon is formed from carbonized thermosetting organic polymer foams that generally have a non-fibrous, open or closed cellular architecture.
  • an electrolytic device is made as schematically depicted in FIG. 1 .
  • the monopolar parallel plate reactor 100 includes a pair of backing plates 102 that confine the plastic cell body panels 104 , typically including one or more flow channels for feeding and/or circulating anolyte or catholyte to the respective anode and cathode compartments 110 and 120 , respectively.
  • Anolyte and catholyte ports 106 and 108 are fluidly coupled to the body panels to deliver the electrolyte to the respective compartments.
  • the anode compartment includes the carbon felt anode 112 that is conductively coupled to the electrical connector 114 .
  • the connector has a grid shape or otherwise provides openings such that anolyte flowing from the panel 104 passes through the connector 114 and carbon felt anode 112 into the cell gap 130 .
  • Treated anolyte that has flown through the carbon felt anode 112 is then withdrawn from the anode compartment through a port (not shown) and recirculated for a desirable number of passes.
  • the arrows indicate the direction of flow of the anolyte and catholyte. Feeding the anolyte that is to be treated is typically performed from a tank or other reservoir (not shown), but may also be implemented by direct feed from a process.
  • the diaphragm 132 that defines the boundary of the cathode and anode compartments in the electrolyte.
  • Cathode 122 is typically mechanically coupled to body panel 104 to complete the electrochemical cell.
  • the catholyte may be circulated through the cathode compartment, which may include a porous or otherwise open-structured cathode to permit catholyte flow through the cathode.
  • the cell may also be constructed as a flow through cell in which the solution to be treated enters the anode compartment and exits the cathode compartment.
  • the term “flow through” means that the anolyte enters one side of the anode at a flow rate and exits the anode at that flow rate on another side, typically traversing the entire cross section of the anode.
  • substantially the entire volume (i.e., greater than 90 vol %, more typically greater than 95 vol %, even more typically greater 99 vol %) of anolyte to be treated will enter the anode on one side and pass through a volume of the anode and exit on the other side.
  • cells with a flow-through anode will typically have an anolyte feed port on one side of the anode and an anolyte withdrawal port on the other side of the anode.
  • the anolyte may also be withdrawn from the cathode compartment (e.g., where the anolyte is in at least temporary fluid communication with the catholyte).
  • suitable electrolytic cells may be configured as monopolar cells or bipolar cells, each or which may be stacked or configured independently of each other.
  • the cell includes a body panel on at least the anode side that is configured such that anolyte is (preferably fed into the body panel and) evenly distributed over one side of the anode.
  • the anolyte may be fed in a continuous flow to the anode compartment or in batches. Where the flow to the anode compartment is discontinuous, it is generally preferred that the anolyte is circulated within the anode compartment such that the anolyte flows through the anode.
  • Suitable containers may have various volumes, and it is generally contemplated that the container (which at least partially encloses the anode and cathode) will have a volume of between about 50 ml to several 100 liters (and even more). Among other things, it should be recognized that the volume of a container will be determined by the volume flow of the solution, the concentration of the contaminant, and the current/voltage applied to the electrodes.
  • the anolyte and the catholyte may be provided to the electrolytic cell in all known manners. Thus, continuous and discontinuous flow are both deemed appropriate. Where desired, at least one of the anolyte and catholyte may also be circulated. However, it is preferred that during operation at least the anolyte will substantially continuously (e.g., at least 90% of the time, and more typically at least 95% of the time) flow through the anode. It should be appreciated that the electrolytes may be moved using any manners known in the art.
  • the electrolytes are pumped at a predetermined flow rate, wherein the electrolyte may be pumped from a reservoir or directly from a process operation (e.g., dying bath, rinsing bath, etc.). Alternatively, at least one of the electrolytes may also be moved by gravity.
  • a process operation e.g., dying bath, rinsing bath, etc.
  • the flow rate of the anolyte through the anode and/or anode compartment may vary considerably and will typically depend on various factors, including the concentration of the contaminant, total anode surface, conductivity of the anolyte, and current density. However, it is generally preferred that the anolyte will pass through the anode at a flow rate of between about 0.01 ml/cm 3 *min to about 100 ml/cm 3 *min, more preferably between about 0.1 ml/cm 3 *min to about 10 ml/cm 3 *min, and most preferably between about 0.5 ml/cm 3 *min to about 3 ml/cm 3 *min (cm 3 reflects bulk volume of carbon felt anode) where the anode is operated under conditions that allow formation of oxidative species.
  • the anolyte is preferably fed to one side of the anode via a distributor structure, which may be integral to the body panel, or may be a dedicated distribution device. Once the anolyte exits the anode, it is contemplated that all manners of withdrawing the anolyte from the anode compartment are deemed suitable for use herein.
  • treated anolyte can be removed from the anolyte compartment using one or more fluid ports that are configured to receive the treated anolyte in a continuous or intermittent manner. The treated anolyte may then be recirculated to the anode for further treatment, stored in a tank, or can be discharged.
  • the flow rate of the catholyte will be determined at least in part by the current density, conductivity, gap width, and other factors that are well within the scope of the person of ordinary skill in the art.
  • the flow rate for the catholyte will be between 0.01 vol % (of the total cathode compartment volume) per hour and 50 vol % per hour (or even more), more typically between 0.1 vol % per hour and 20 vol % per hour, and most typically between 0.5 vol % per hour and 10 vol % per hour.
  • circulation of the catholyte may not be needed or may only be temporary. With respect to feeding and withdrawing the catholyte, the same considerations as for the anolyte apply.
  • the anode material comprises carbon felt produced from an organic textile material via carbonization (see above).
  • the carbon felt will have a thickness of between about 0.1 cm and 10 cm (and in some cases even more), and even more preferably between about 0.5 cm and 5 cm, while the width and length are generally dependent on the particular electrolytic cell configuration.
  • appropriate anode thicknesses and material parameters will at least in part be determined by the backpressure generated by the anode and desired flow rate.
  • anode is fabricated from porous carbonaceous materials, including glassy carbon and similar materials so long as such materials allow anolyte flow through the carbonaceous material (e.g., via network of interconnecting pores or channels) at a rate sufficient to reduce or even eliminate oxidative carbon degradation when the anode is operated under conditions that generate oxidative species.
  • Suitable alternative anode materials include fabrics/webbings that include activated carbon fibers, graphite felt, and any reasonable combination thereof.
  • Still further contemplated anode materials also include composite materials that include the felt or other carbonaceous materials.
  • suitable anodes may be manufactured from a conductive polymer that is coated, or in which is embedded carbon felt or other carbonaceous materials.
  • cathodes may vary substantially, and a particular choice for the cathode material and configuration will typically depend on the particular solution and/or contaminant that is to be treated.
  • appropriate cathode materials are electrochemically relatively inert. Therefore, especially preferred cathode materials include platinum-coated titanium.
  • numerous other metals, metal alloys, and even carbon are considered suitable for use herein.
  • the cathode material and configuration may be identical with the anode material and configuration. Therefore, the cathode may have numerous configurations, and may include materials and configurations in which the solution can pass through the cathode, as well as impermeable materials and configurations.
  • the anolyte that includes the contaminant is an aqueous solution having a substantially neutral pH, typically between about 5.5 and 8.5, more typically between about 6.0 and 8.0, and most typically between about 6.5 and 7.5).
  • a substantially neutral pH typically between about 5.5 and 8.5, more typically between about 6.0 and 8.0, and most typically between about 6.5 and 7.5.
  • more alkaline or more acidic solutions may also be desired, especially where the so desired pH will increase solubility of the contaminant or oxidation product(s) of the contaminant.
  • anolytes need not be restricted to purely aqueous solutions, and non-aqueous solutions are also expressly contemplated, including those comprising emulsifiers, organic solvents, and even liquefied gases.
  • waste streams form an industrial process, wherein such solutions are either circulated between the process and the electrochemical cell (which may further include use of a reservoir), or be directly fed from the process to the electrolytic cell.
  • exemplary processes and sources include rinsing or washing operations (e.g., from fruit or animal processing plant, or from metal plating operations), sterilization, cooling/heating water, aqueous solvents for chemical (e.g., chromatography supplies, buffers, etc.) and/or biological processes (e.g., fermentations, enzymatic reactions, etc.).
  • a contaminant may vary substantially.
  • contemplated contaminants include bacteria (including spores), viruses, eukaryotic cells, halogenated (typically aromatic) organic compounds, dyes or otherwise colored compounds, and all organic matter directly or indirectly derived from contact of the organic matter with water. Therefore, it should be recognized that the pH of suitable solutions may vary, and it is generally preferred that electrolysis according to the inventive subject matter will be in the neutral pH range. Suitable pH values may be adjusted by adding acid or base, or a buffer system to the anolyte.
  • the solution may further be modified to increase and/or decrease conductivity. Where conductivity is increased, all known salts (preferably with insignificant interference [e.g., electroplating] to the electrolytic process) are considered suitable herein. Similarly, the solution may also be diluted, or otherwise reduced in conductivity (e.g., precipitation, chemical modification, or filtration of conductive species in the solution).
  • the current and/or voltage of contemplated systems will vary substantially, and all currents and/or voltages suitable for reduction of the contaminant are considered appropriate for use herein.
  • typical voltages will be in the range of 0-100 Volt, and more typically between 10 Volt and 50 Volt, at currents of between about 1 mA (or even less) and 100 A and higher, and more typically between about 0.1 A and 10 A.
  • current densities will preferably be in the range of about 1 mA/cm 2 and 1000 mA/cm 2 , more preferably between about 10 mA/cm 2 and 500 mA/cm 2 , and most typically between about 30 mA/cm 2 and 100 mA/cm 2 .
  • the term “about” in conjunction with a numeral refers to a range of that numeral starting from 10% below the absolute of the numeral to 10% above the absolute of the numeral, inclusive.
  • the term “about 10 A/cm 2 ” refers to a range of 9 mA/cm 2 to 11 mA/cm 2 .
  • the contaminant may be oxidized directly at the anode, or indirectly via an oxidative species.
  • the current density will be adjusted such that oxidative species are formed in the particular anolyte.
  • preferred species include ozone, hydrogen peroxide, hydroxy radicals, oxygen ions, superoxide anions, singlet oxygen, etc. It is contemplated that formation of such oxidative species will provide for reactive molecules that then oxidize the contaminant.
  • the contaminant is predominantly oxidized (i.e., at least 51% of the contaminants, more typically at least 70% of the contaminants, and most typically 85-90% of the contaminants) via such reactive species produced from the aqueous solution rather than being directly oxidized on the anode.
  • the inventors performed numerous experiments to generate oxidative species, and in some cases to also perform direct oxidation of various compounds. While generation of oxygen was relatively simple to observe, the detection of hydroxyl radicals, ozone, peroxide, and other oxidative species typically requires expensive and sophisticated equipment. Therefore, the inventors decided to indirectly detect oxidative species by adding materials to the water that react with or capture these species. Initially it was believed that small amounts of chloride ions were being converted to hypochlorite, which could act as the oxidizing agent. However, subsequent experiments with de-ionized water conclusively demonstrated that hypochlorite was not formed in an amount sufficient to react with oxidizable molecules. Instead, it was found that all or almost all of the contemplated configurations and methods allowed for the generation of reactive species that indirectly oxidized contaminants. In some cases, direct oxidation of the contaminant was also observed.
  • carbon felt materials made from dehydrogenation of long chain organic structures remained intact, even when continuously operated for prolonged periods (e.g., more than 2 hours, more typically more than 6 hours, even more typically more than 24 hours, and most typically more than 48 hours) at currents of 50 mA/cm 2 (cm 2 representing the gross dimensions of anode felt portion, not actual surface area), which indicates that oxygen and other oxidizing species were generated at higher overpotentials than carbon dioxide formation from the carbon at the electrodes.
  • certain carbon black and graphitic structures were oxidized at significant rates (especially where no flow-through configuration was implemented).
  • An electrochemical cell was constructed as a monopolar parallel plate reactor similar to the device of FIG. 1 .
  • the anode was made by attaching a carbon felt pad to a predrilled graphite feeder plate.
  • the carbon felt was 10 cm by 4 cm, and 1 cm thick.
  • the cathode was a flat titanium plate coated with platinum.
  • the cell gap (distance between carbon felt and the cathode) was 14 mm. The flow through the cell was arranged so that the treated water flowed out of the top of the cell after flowing through the felt in the anode compartment.
  • the flow rate was adjusted to 30 ml/min to correspond with a once through treatment which removed the color and odor from the water in the exiting stream.
  • the water was dosed with 2 g/liter of sodium sulfate to increase the conductivity.
  • the experiments were conducted at room temperature. The water was first pumped through the anode compartment with the current off and samples taken to check for concentrations of the target contaminant, This ensured that the inventors would not observe effects based on adsorption onto the high surface area felt.
  • a constant current of 3.0 A was used at various voltages, depending on the particular experiment. Typical voltages were about 12 volts, with the actual voltage being predominantly determined by the cell gap and electrolyte conductivity.
  • Acid violet 7B a common triphenylene dye identified by reference to the Color Index as number 42745 was added to deionized water at a concentration of 100 milligrams per liter. Deionized water was made conductive with addition of 2 grams per liter of sodium sulfate. This solution was pumped through the anode compartment described above with the current off. The dye concentration remained the same. A 3.0 amps current was then applied to the cell and the solution pumped through at the rate of 30 ml per minute. Remarkably, the solution was completely decolorized as it exited the cell. The experiment was repeated with Allura Red AC, a common foodstuff dye identified as CI # 16035, and later with Brilliant Green #42040 in the Color Index with the same results.
  • PCB Perchlorobiphenyl
  • DDT (1,1-Bis-(p-chlorophenyl)-2,2,2-trichloroethane) extracted from an old disused spray containing the organophosphate pesticide Methidathion (O,O-Dimethyl S-(5-methoxy-1,3,4-thiadiazolinyl-3-methyl)dithiophosphate) was added to the test solution producing a solution which on analysis gave 53 ppm of DDT. After passing through the anode compartment without electrolysis, the concentration was found to be 54 ppm, while no DDT was detected and after electrolysis of the solution in the electrolytic anode compartment.
  • Methidathion O,O-Dimethyl S-(5-methoxy-1,3,4-thiadiazolinyl-3-methyl
  • sodium sulfate (2 grams per liter) was added as a current carrier. The cell was run at 3 amps, and the resultant treated liquors became clear on standing for 30 minutes with brown sediment of insoluble oxidized organics at the bottom of the liquors. There was no odor from the treated liquors either immediately after treatment or after 4 weeks. It should be noted that the addition rate of sodium sulfate could be lessened or entirely omitted by closer spacing of the electrodes.
  • wash water from an apple packing plant containing pesticide residues, organic acids and fermentation products was treated in the cell in an arrangement as schematically depicted in FIG. 2 .
  • the initial solution was blue green in color with a strong odor.
  • the color and odor disappeared.
  • After settling the treated solution a brown sediment precipitated, which was found to be sterile.
  • contemplated devices and methods may be employed for the (preferably continuous) sterilization of the effluent from septic tanks without the many problems otherwise associated with hypochlorite handling.
  • the devices and methods according to the inventive subject matter may also be employed for self cleaning swimming pool water sterilizers in which both the anode and cathode are made from carbon felt and are electrochemically reversed to inhibit growth of calcium salts on the cathode.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
US11/994,967 2005-07-07 2006-07-07 Methods and Apparatus for Generating Oxidizing Agents Abandoned US20090152123A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/994,967 US20090152123A1 (en) 2005-07-07 2006-07-07 Methods and Apparatus for Generating Oxidizing Agents

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US69745505P 2005-07-07 2005-07-07
US11/994,967 US20090152123A1 (en) 2005-07-07 2006-07-07 Methods and Apparatus for Generating Oxidizing Agents
PCT/US2006/026338 WO2007008591A2 (fr) 2005-07-07 2006-07-07 Procedes et dispositif de production d'oxydants

Publications (1)

Publication Number Publication Date
US20090152123A1 true US20090152123A1 (en) 2009-06-18

Family

ID=37637744

Family Applications (1)

Application Number Title Priority Date Filing Date
US11/994,967 Abandoned US20090152123A1 (en) 2005-07-07 2006-07-07 Methods and Apparatus for Generating Oxidizing Agents

Country Status (3)

Country Link
US (1) US20090152123A1 (fr)
AU (1) AU2006269410B2 (fr)
WO (1) WO2007008591A2 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120138478A1 (en) * 2010-12-03 2012-06-07 Electrolytic Ozone Inc. Electrolytic Cell for Ozone Production
CN102745794A (zh) * 2011-04-21 2012-10-24 北京市自来水集团有限责任公司 一种饮用水电化学预氧化装置及方法
US20130029016A1 (en) * 2010-04-22 2013-01-31 Koninklijke Philips Electronics N.V. Beverage carbonator and method for producing such carbonated beverage
US20130087466A1 (en) * 2011-10-07 2013-04-11 Robert Brian Dopp Electrochemical digestion of organic molecules
WO2014039929A1 (fr) * 2012-09-07 2014-03-13 Clean Chemistry, Llc Systèmes et procédés permettant de générer des espèces réactives de l'oxygène et applications associées
US9145615B2 (en) 2010-09-24 2015-09-29 Yumei Zhai Method and apparatus for the electrochemical reduction of carbon dioxide
WO2016126694A1 (fr) * 2015-02-02 2016-08-11 T+Ink, Inc. Système de création de produits d'assainissement
US9551076B2 (en) 2011-05-31 2017-01-24 Clean Chemistry, Inc. Electrochemical reactor and process
WO2014136063A3 (fr) * 2013-03-06 2017-05-04 Krupakar Murali Subramanian Systèmes et procédés de génération et de collecte d'espèces réactives
US10259729B2 (en) 2014-09-04 2019-04-16 Clean Chemistry, Inc. Systems and method of water treatment utilizing reactive oxygen species and applications thereof
US20190292075A1 (en) * 2018-03-21 2019-09-26 Innovative Water Care, Llc Method of Removing Pesticides from Wastewater
US10472265B2 (en) 2015-03-26 2019-11-12 Clean Chemistry, Inc. Systems and methods of reducing a bacteria population in high hydrogen sulfide water
US10611656B2 (en) 2015-12-07 2020-04-07 Clean Chemistry, Inc. Methods of microbial control
US10883224B2 (en) 2015-12-07 2021-01-05 Clean Chemistry, Inc. Methods of pulp fiber treatment
US11001864B1 (en) 2017-09-07 2021-05-11 Clean Chemistry, Inc. Bacterial control in fermentation systems
US11136714B2 (en) 2016-07-25 2021-10-05 Clean Chemistry, Inc. Methods of optical brightening agent removal
US11311012B1 (en) 2017-09-07 2022-04-26 Clean Chemistry, Inc. Bacterial control in fermentation systems

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007033445A1 (de) * 2007-07-18 2009-01-22 Monopharm Handelsgesellschaft Mbh Diaphragmalyse-Verfahren und Verwendung der nach dem Verfahren erhaltenen Produkte
US10450667B2 (en) 2014-10-27 2019-10-22 International Business Machines Corporation System for treating solution for use in electroplating application and method for treating solution for use in electroplating application
CN109904390A (zh) * 2019-01-28 2019-06-18 武汉理工大学 一种金属锂/镀镍碳布复合负极的制备方法

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975246A (en) * 1973-06-09 1976-08-17 Sachs-Systemtechnik Gmbh Method of disinfecting water
US4285831A (en) * 1976-10-05 1981-08-25 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4319973A (en) * 1977-12-06 1982-03-16 Battelle Memorial Institute Method and machine for washing and bleaching textiles
US4445990A (en) * 1981-11-12 1984-05-01 General Electric Company Electrolytic reactor for cleaning wastewater
US4505797A (en) * 1983-03-24 1985-03-19 Ionics, Incorporated Ion-exchange membranes reinforced with non-woven carbon fibers
US4556469A (en) * 1981-11-12 1985-12-03 General Electric Environmental Services, Inc. Electrolytic reactor for cleaning wastewater
US5624545A (en) * 1993-06-28 1997-04-29 Eka Nobel Inc. Production of polysulphide by electrolysis of white liquor containing sulphide
US5662789A (en) * 1995-03-03 1997-09-02 National Research Council Of Canada Removal of organics from aqueous solutions
US5770037A (en) * 1996-11-21 1998-06-23 Konica Corporation Water processing method
US5904832A (en) * 1996-12-20 1999-05-18 Huron Tech Canada, Inc. Regeneration of active carbon and polymeric adsorbents
US6315886B1 (en) * 1998-12-07 2001-11-13 The Electrosynthesis Company, Inc. Electrolytic apparatus and methods for purification of aqueous solutions
US20030082095A1 (en) * 2001-10-22 2003-05-01 Halox Technologies, Inc. Electrolytic process and apparatus
US6673229B2 (en) * 2000-07-05 2004-01-06 Sony International (Europe) Gmbh Electrochemical apparatus and process for purification of fluids
US6984303B2 (en) * 2003-02-25 2006-01-10 Noveon Ip Holdings Corp. Electrochemical production of dyes using graphite felt electrodes

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975246A (en) * 1973-06-09 1976-08-17 Sachs-Systemtechnik Gmbh Method of disinfecting water
US4285831A (en) * 1976-10-05 1981-08-25 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4319973A (en) * 1977-12-06 1982-03-16 Battelle Memorial Institute Method and machine for washing and bleaching textiles
US4445990A (en) * 1981-11-12 1984-05-01 General Electric Company Electrolytic reactor for cleaning wastewater
US4556469A (en) * 1981-11-12 1985-12-03 General Electric Environmental Services, Inc. Electrolytic reactor for cleaning wastewater
US4505797A (en) * 1983-03-24 1985-03-19 Ionics, Incorporated Ion-exchange membranes reinforced with non-woven carbon fibers
US5624545A (en) * 1993-06-28 1997-04-29 Eka Nobel Inc. Production of polysulphide by electrolysis of white liquor containing sulphide
US5662789A (en) * 1995-03-03 1997-09-02 National Research Council Of Canada Removal of organics from aqueous solutions
US5770037A (en) * 1996-11-21 1998-06-23 Konica Corporation Water processing method
US5904832A (en) * 1996-12-20 1999-05-18 Huron Tech Canada, Inc. Regeneration of active carbon and polymeric adsorbents
US6315886B1 (en) * 1998-12-07 2001-11-13 The Electrosynthesis Company, Inc. Electrolytic apparatus and methods for purification of aqueous solutions
US6328875B1 (en) * 1998-12-07 2001-12-11 Zappi Water Purification System, Inc., Electrolytic apparatus, methods for purification of aqueous solutions and synthesis of chemicals
US6673229B2 (en) * 2000-07-05 2004-01-06 Sony International (Europe) Gmbh Electrochemical apparatus and process for purification of fluids
US20030082095A1 (en) * 2001-10-22 2003-05-01 Halox Technologies, Inc. Electrolytic process and apparatus
US6984303B2 (en) * 2003-02-25 2006-01-10 Noveon Ip Holdings Corp. Electrochemical production of dyes using graphite felt electrodes

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130029016A1 (en) * 2010-04-22 2013-01-31 Koninklijke Philips Electronics N.V. Beverage carbonator and method for producing such carbonated beverage
US9145615B2 (en) 2010-09-24 2015-09-29 Yumei Zhai Method and apparatus for the electrochemical reduction of carbon dioxide
CN103328690B (zh) * 2010-12-03 2016-08-31 电解臭氧有限公司 用于臭氧生成的电解池
CN103328690A (zh) * 2010-12-03 2013-09-25 电解臭氧有限公司 用于臭氧生成的电解池
US20120138478A1 (en) * 2010-12-03 2012-06-07 Electrolytic Ozone Inc. Electrolytic Cell for Ozone Production
US8980079B2 (en) * 2010-12-03 2015-03-17 Electrolytic Ozone, Inc. Electrolytic cell for ozone production
CN102745794A (zh) * 2011-04-21 2012-10-24 北京市自来水集团有限责任公司 一种饮用水电化学预氧化装置及方法
CN102745794B (zh) * 2011-04-21 2015-01-21 北京市自来水集团有限责任公司 一种饮用水电化学预氧化装置及方法
US10577698B2 (en) 2011-05-31 2020-03-03 Clean Chemistry, Inc. Electrochemical reactor and process
US9551076B2 (en) 2011-05-31 2017-01-24 Clean Chemistry, Inc. Electrochemical reactor and process
AU2012318934B2 (en) * 2011-10-07 2017-07-27 Robert Brian Dopp Electrochemical digestion of organic molecules
US10407322B2 (en) * 2011-10-07 2019-09-10 Robert Brian Dopp Electrochemical digestion of organic molecules
US20130087466A1 (en) * 2011-10-07 2013-04-11 Robert Brian Dopp Electrochemical digestion of organic molecules
US9517956B2 (en) 2012-09-07 2016-12-13 Clean Chemistry, Llc System and method for generation of point of use reactive oxygen species
US9517955B2 (en) 2012-09-07 2016-12-13 Clean Chemistry, Llc System and method for generation of point of use reactive oxygen species
WO2014039929A1 (fr) * 2012-09-07 2014-03-13 Clean Chemistry, Llc Systèmes et procédés permettant de générer des espèces réactives de l'oxygène et applications associées
US10875799B2 (en) * 2012-09-07 2020-12-29 Clean Chemistry, Inc. System and method for generation of point of use reactive oxygen species
US10501346B2 (en) * 2012-09-07 2019-12-10 Clean Chemistry, Inc. System and method for generation of point of use reactive oxygen species
WO2014136063A3 (fr) * 2013-03-06 2017-05-04 Krupakar Murali Subramanian Systèmes et procédés de génération et de collecte d'espèces réactives
US10875798B2 (en) 2014-09-04 2020-12-29 Clean Chemistry, Inc. Systems and method for oxidative treatment utilizing reactive oxygen species and applications thereof
US10259729B2 (en) 2014-09-04 2019-04-16 Clean Chemistry, Inc. Systems and method of water treatment utilizing reactive oxygen species and applications thereof
US11827543B2 (en) 2014-09-04 2023-11-28 Clean Chemistry, Inc. Method for continuous supply of superoxide-containing peracetate oxidant solution
WO2016126694A1 (fr) * 2015-02-02 2016-08-11 T+Ink, Inc. Système de création de produits d'assainissement
US10941063B2 (en) 2015-03-26 2021-03-09 Clean Chemistry, Inc. Method for down-hole treatment of a production well for sulfur based contaminants
US10472265B2 (en) 2015-03-26 2019-11-12 Clean Chemistry, Inc. Systems and methods of reducing a bacteria population in high hydrogen sulfide water
US10611656B2 (en) 2015-12-07 2020-04-07 Clean Chemistry, Inc. Methods of microbial control
US10883224B2 (en) 2015-12-07 2021-01-05 Clean Chemistry, Inc. Methods of pulp fiber treatment
US11111629B2 (en) 2015-12-07 2021-09-07 Clean Chemistry, Inc. Methods of pulp fiber treatment
US11225755B2 (en) 2015-12-07 2022-01-18 Clean Chemistry, Inc. Methods of paper mill processing using recycled white water with microbial control
US11795615B2 (en) 2015-12-07 2023-10-24 Clean Chemistry, Inc. Methods of pulp fiber treatment
US11136714B2 (en) 2016-07-25 2021-10-05 Clean Chemistry, Inc. Methods of optical brightening agent removal
US11001864B1 (en) 2017-09-07 2021-05-11 Clean Chemistry, Inc. Bacterial control in fermentation systems
US11311012B1 (en) 2017-09-07 2022-04-26 Clean Chemistry, Inc. Bacterial control in fermentation systems
WO2019182883A1 (fr) * 2018-03-21 2019-09-26 Innovative Water Care, Llc Procédé d'élimination de pesticides présents dans les eaux usées
US10961134B2 (en) * 2018-03-21 2021-03-30 Innovative Water Care, Llc Method of removing pesticides from wastewater
US20190292075A1 (en) * 2018-03-21 2019-09-26 Innovative Water Care, Llc Method of Removing Pesticides from Wastewater

Also Published As

Publication number Publication date
WO2007008591B1 (fr) 2007-08-02
AU2006269410B2 (en) 2009-07-02
WO2007008591A9 (fr) 2007-06-14
AU2006269410A1 (en) 2007-01-18
WO2007008591A2 (fr) 2007-01-18
WO2007008591A3 (fr) 2007-05-03

Similar Documents

Publication Publication Date Title
AU2006269410B2 (en) Methods and apparatus for generating oxidizing agents
Martínez-Huitle et al. A critical review over the electrochemical disinfection of bacteria in synthetic and real wastewaters using a boron-doped diamond anode
Ghernaout et al. From chemical disinfection to electrodisinfection: The obligatory itinerary?
AU767548B2 (en) Electrolytic apparatus, methods for purification of aqueous solutions and synthesis of chemicals
Kerwick et al. Electrochemical disinfection, an environmentally acceptable method of drinking water disinfection?
US6315886B1 (en) Electrolytic apparatus and methods for purification of aqueous solutions
Drogui et al. Oxidising and disinfecting by hydrogen peroxide produced in a two-electrode cell
RU2119802C1 (ru) Установка для электрохимической обработки жидкой среды (варианты)
US6773575B2 (en) Electrolytic cell and process for the production of hydrogen peroxide solution and hypochlorous acid
CN107129011B (zh) 一种电解—离子膜耦合处理高氯盐有机废水的装置及方法
CN1181977A (zh) 电解功能水、其制造方法及制造装置
KR101220891B1 (ko) 3차원 다공성 복극 전극 및 이를 구비한 전기살균 필터와 이를 이용한 수처리 방법
DE10216860A1 (de) Elektrolysezelle für die Herstellung von Wasserstoffperoxid und Verfahren zur Herstelung von Wasserstoffperoxid
Pattabhi et al. Electrochemical degradation of reactive red 195 from its aqueous solution using RuO2/IrO2/TaO2 coated titanium electrodes
Uğurlu et al. Experimental Investigation of Chemical Oxygen Demand, Lignin and Phenol Removal from Paper Mill Effluents Using Three-Phase Three-Dimensional Electrode Reactor.
CN105664525B (zh) 从液体中吸附污染物以及吸附剂的电化学再生
KR102013864B1 (ko) 전기분해수 및 uv 처리를 이용하는 유기물의 고도 산화 방법
EP2089326B1 (fr) Système de traitement de l'eau de ballast des navires, des plates-formes pétrolières en mer et de contenants, en général, à l'aide d'un procédé dans un réacteur électrochimique
Chang et al. Study on the efficacy of sterilization in tap water by electrocatalytic technique
Sudeep et al. A study on the degradation of synthetic dyes using tubular electrochemical reactor.
JP2002053990A (ja) 過酸化水素水の製造方法
JP2008200667A (ja) 水の脱臭、脱色、殺菌処理方法及び装置
Awad Abouelata Fundamentals and Functional Mechanisms of Electrocatalysis in Water Treatment
JPH08267073A (ja) 染色廃水の処理装置における電極装置
Abdelhay et al. Corrected Proof

Legal Events

Date Code Title Description
AS Assignment

Owner name: APPLIED INTELLECTUAL CAPITAL, NEVADA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BUTLER, DEAN;CLARKE, ROBERT LEWIS;REEL/FRAME:018236/0571;SIGNING DATES FROM 20060809 TO 20060905

AS Assignment

Owner name: AIC NEVADA INC.,CALIFORNIA

Free format text: MERGER;ASSIGNOR:APPLIED INTELLECTUAL CAPITAL;REEL/FRAME:021720/0438

Effective date: 20080311

Owner name: AIC NEVADA INC., CALIFORNIA

Free format text: MERGER;ASSIGNOR:APPLIED INTELLECTUAL CAPITAL;REEL/FRAME:021720/0438

Effective date: 20080311

AS Assignment

Owner name: APPLIED INTELLECTUAL CAPITAL LIMITED

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:AIC NEVADA, INC.;REEL/FRAME:022593/0028

Effective date: 20090424

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION