US20110079520A1 - Method and Apparatus for the Electrochemical Treatment of Liquids Using Frequent Polarity Reversal - Google Patents

Method and Apparatus for the Electrochemical Treatment of Liquids Using Frequent Polarity Reversal Download PDF

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US20110079520A1
US20110079520A1 US12/895,197 US89519710A US2011079520A1 US 20110079520 A1 US20110079520 A1 US 20110079520A1 US 89519710 A US89519710 A US 89519710A US 2011079520 A1 US2011079520 A1 US 2011079520A1
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liquid
electrodes
treatment
liquid treatment
treatment method
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US12/895,197
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James A. Tretheway
Brian R. Hale
Ajit K. Chowdhury
Jeremy J. Vogel
Dennis E. Bahr
Myron F. Miller
Karl W. Marschke
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BioIonix Inc
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BioIonix Inc
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Assigned to BIOIONIX, INC. reassignment BIOIONIX, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MILLER, MYRON F., BAHR, DENNIS E., CHOWDHURY, AJIT K., HALE, BRIAN R., MARSCHKE, KARL W., TRETHEWAY, JAMES A., VOGEL, JEREMY J.
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/32Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with electric currents without heating effect
    • A23L3/325Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with electric currents without heating effect by electrolysis
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/03Electric current
    • A61L2/035Electrolysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46133Electrodes characterised by the material
    • C02F2001/46138Electrodes comprising a substrate and a coating
    • C02F2001/46142Catalytic coating
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/305Endocrine disruptive agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/42Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/002Construction details of the apparatus
    • C02F2201/003Coaxial constructions, e.g. a cartridge located coaxially within another
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/4611Fluid flow
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/46115Electrolytic cell with membranes or diaphragms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/4612Controlling or monitoring
    • C02F2201/46125Electrical variables
    • C02F2201/4613Inversing polarity
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/04Oxidation reduction potential [ORP]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/29Chlorine compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/04Flow arrangements
    • C02F2301/043Treatment of partial or bypass streams
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/04Flow arrangements
    • C02F2301/046Recirculation with an external loop
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/04Disinfection
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to an apparatus for treating liquids to disinfect and oxidize contaminants and in particular to a method and apparatus of this type using frequent polarity reversal of the power applied to the electrodes.
  • Liquids including water and solvent based ones, are capable of being treated by many different methods known the in art. Biological methods can disinfect and oxidize, but require long treatment times, a large equipment footprint and other complications. Such methods are commonly used to treat municipal wastewater but have had limited application in liquid treatment at the industrial scale.
  • the treatment of liquid streams through the addition of disinfecting chemicals such as chlorine or bromine is also well-known.
  • disinfecting chemicals such as chlorine or bromine
  • the class of chlorine disinfectants includes chlorine gas, hypochlorous acid, sodium hypochlorite, and chlorine dioxide. These chemicals typically are purchased in bulk, with attendant cost, storage and dosing issues. Chlorine gas has significant safety and security issues associated with it.
  • Chlorine is often used because of its low cost. But in some applications, for example in chiller water, cold brine and flume water used in poultry, meat and vegetable processing, the addition of these chemicals may be disfavored because of concerns about the generation of off-taste in the product and chemical byproducts that may adversely affect product quality, plant personnel or the environment. Chlorine's efficacy is also dramatically affected by pH levels, oftentimes requiring additional pH adjustment that adds to cost and operating complications. As another disadvantage, chlorine dosage requirements in some applications can be very high due to high organic loads and pathogen levels. High dosages of these chemicals make the process difficult to control to maintain reliable disinfection without generating excessive unwanted chlorinated byproducts, such as trichloramines. They also make it difficult to maintain residual chlorine levels within the levels that may be permitted by the United States Department of Agriculture (USDA) or other application-specific regulations.
  • USDA United States Department of Agriculture
  • UV light is sometimes used for water and wastewater final effluent disinfection.
  • a significant drawback to ultraviolet systems is their inability to work in turbid liquids with suspended solids or color.
  • Electroporation is a high voltage, low current process that disinfects by penetrating the cell walls of pathogens and either destroying or inactivating them. Electroporation has many laboratory scale uses, including for the insertion of genes in cells, but has not scaled up well to industrial use due to the high voltages used and other reasons.
  • Direct current electrolytic processes have also been demonstrated to disinfect contaminants in liquids.
  • electrolysis comparatively low voltage, high current electrical power is passed through the liquid, breaking bonds in chemical compounds and causing destructive changes to biological cells. Depending on the application, this can be a more energy efficient method.
  • Electrolytic systems called hypochlorite generators have been used commercially for indirect disinfection of liquids. Electrodes are immersed in a relatively pure salt water solution and direct current is applied to generate hypochlorite. The hypochlorite-enhanced solution is then injected into the liquid stream to be treated. Such systems typically use different anode and cathode materials. They have the same issues with pH control as with the direct addition of hypochlorite.
  • Another electrolytic method uses an ion exchange membrane in a salt solution between direct current electrodes to create separate acidic anolyte and alkaline catholyte solutions with purported electrochemically activated properties. Sometimes these two liquids are used separately for cleaning, or sometimes may be combined and marketed under rather fanciful names implying health and longevity effects.
  • Another electrolytic process is used to directly treat swimming pool water to which salt is added. Since swimming pool liquid is less controlled regarding contaminants, the polarity is reversed on the electrodes, typically every few hours, to reduce electrode fouling caused by the electrochemical deposition of materials onto the electrodes.
  • electrolytic systems use plate or expanded metal electrodes that typically are spaced 0.5-2 mm apart. Any polarity reversal is done only very infrequently, typically 2-6 hours between reversals.
  • the anodes typically use one or more metal oxides from the platinum group metals as a coating over a valve metal such as titanium. It has generally been observed that polarity reversing power is highly destructive to these coatings with various mechanisms of failure being described including hydrogen embrittlement when the electrode is operated as a cathode.
  • the present invention provides direct, high flow rate, electrical treatment of liquids with significant organic loads and suspended solids, including but not limited to poultry chiller water and processed meats chiller brine. While the inventors do not wish to be bound by a particular theory, it is believed that such direct treatment may provide significant advantages in exposing the water to short-lived chemical species. The possibility of such direct treatment required a determination that treatment effectivity could be maintained for relatively large electrode gaps (5 mm or larger) and without debilitating electrodes fouling, both empirically confirmed by the present inventors.
  • the present invention provides a liquid treatment system with a first and second electrode having a comparatively large separation between them that permits the passage of a significantly large volume of liquid that may contain small solids.
  • a polarity reversing power supply is connected across the first and second electrodes, the power supply switching the polarity of the voltage at a period determined empirically for each liquid being treated within a specified range.
  • the inventors have determined that there is an optimum narrow frequency range around 0.03 Hz for high performance duplex stainless steel electrodes above or below which a substantial reduction of treatment performance occurs for a particular liquid stream. This equates to a polarity reversal approximately every 17 seconds. In addition, the disinfection falls off rapidly when the period between polarity reversals is less than 5 seconds (0.1 Hz) or greater than 50 seconds (0.01 Hz).
  • the inventors have determined that for catalytic platinum group metal electrodes, the detrimental effects of frequent polarity reversal on electrode life can be balanced against the need to change polarities to prevent electrode fouling and that the optimal time between polarity reversals is approximately between 10 seconds and 60 minutes, depending on the composition of the liquid stream.
  • electrolysis degrades many metals and their oxides when used for electrolysis.
  • Very high levels of metal ions such as chromium, nickel, iron, and tin are found in liquids that have been treated with electrode materials containing them. This prevents conventional electrolysis with such electrodes from being used in applications where metal toxicity is a concern. They remain quite appropriate for various other treatment applications, such as electrowinning and electro-flocculation.
  • catalytic electrodes for example those from the platinum group metals and metal oxides, do not dissolve into the liquid under polarity reversing electrolysis to any measurable extent.
  • catalytic electrode surfaces including those from the platinum group metals and metal oxides, and from the doped diamond category.
  • Polarity reversal can be controlled to provide different times between polarity reversal for each specific electrode surface, enabling the control system to tailor the reactive species being generated to meet the needs of a particular liquid stream being treated.
  • a fluid is continuously recirculated at high flow rates for another purpose, such as cooling a product and rechilling the liquid to maintain its desired temperature.
  • the inventors have shown that in many cases a proportionally smaller liquid flow is all that is required to maintain the desired level of treatment in the liquid, reducing the size of the electrolytic treatment cell, associated piping and other components.
  • the liquid stream is directly discharged and is not recycled for another reason.
  • the desired treatment level may be difficult to achieve at reasonable equipment cost in a single pass.
  • the inventors have determined that recycling a portion of the treated liquid back to the treatment cell can have a synergistic effect on process efficacy.
  • a method for oxidizing and destroying trace pharmaceuticals and personal care products is disclosed.
  • PPCP pharmaceutical and personal care product
  • disinfection efficacy a low cost, easily measured value, serves as a robust surrogate for the efficacy of removal of trace pharmaceuticals and personal care product residuals.
  • the inventors have determined that for liquid streams without significant bacterial load, a safe, food grade bacteria like Lactobacillus Acidophilus, used to make yogurt, can be added to the liquid to provide this surrogate disinfection measure.
  • This electrochemical process produces oxygen at the anode and hydrogen at the cathode. With the polarity reversal of this process, each electrode in a pair alternates between generating hydrogen and oxygen.
  • FIG. 1 is a perspective view of a liquid treatment system in one embodiment of the present invention showing a main housing holding opposed planar electrodes between liquid inlets and outlets, a power distribution module, and a control unit;
  • FIG. 2 is a detailed block diagram of the components of FIG. 1 showing the electrodes as flat plates;
  • FIGS. 3 a and 3 b are graphs of disinfection versus frequency showing a preferred range of operation of the present invention for stainless steel and catalytic electrodes;
  • FIG. 4 is a simplified representation of a method to disinfect processed meat and processed poultry products immediately after a cooking cycle to rapidly cool them for further processing, packaging or storage;
  • FIG. 5 is a simplified representation of a method to disinfect raw poultry chiller water to rapidly cool the birds for further processing, packaging or storage;
  • FIG. 6 is a simplified representation of a method to disinfect water used to wash and chill vegetables and fruits, such as cut leafy greens, to help ensure the safety of the product and permit extended reuse of the water;
  • FIG. 7 is a graph of performance achieved with the method of the patent for removing trace pharmaceuticals from wastewater showing the strong correlation of trace pharmaceutical destruction with bacterial disinfection performance on this same liquid;
  • FIG. 8 is a graph of performance achieved with the method of the patent for removing trace personal care product residuals from wastewater showing the strong correlation of trace personal care product destruction with bacterial disinfection performance on this same liquid;
  • FIG. 9 is a simplified representation of an alternate electrode arrangement using a rod and cylinder configuration
  • a liquid treatment system 10 per the present invention may include a treatment unit 12 providing a liquid inlet 14 and outlet 16 to conduct liquid across internal electrodes 28 .
  • the electrodes 28 are contained in an insulating housing 18 supported on frame 20 .
  • a power distribution module 22 provides electrical connections 24 to the internally contained electrodes 28 for power received from a control unit 26 .
  • the control unit 26 has a touchscreen user interface 27 for the display and entry of data including critical operation parameters.
  • the treatment unit 12 includes two or more generally planar and parallel electrodes 28 held in a channel 36 between the inlet 14 and the outlet 16 .
  • the electrodes 28 are separated along an axis 30 generally perpendicular to the flow of liquid by gaps 32 to receive the influent liquid 34 therethrough.
  • the separation of the electrodes 28 will be greater than 5 mm to permit the passage of influent liquid 34 without undue risk of clogging.
  • One or more chemical sensors 40 may be positioned in sensor fitting 38 downstream from the electrodes 28 and channel 36 to measure chemical properties of the liquid and/or a flow sensor 42 may be positioned in the influent liquid 34 or effluent liquid 35 to measure the flow across the electrodes 28 .
  • the chemical sensors 40 may include those measuring pH, oxidation-reduction potential, chlorine level, free chlorine level, or total chlorine level.
  • the amount of flow through the channel 36 may be controlled by an electrically driven pump 44 and/or valve 46 alone or in combination.
  • the electrodes 28 are electrically isolated from each other as held by the housing 18 but may be joined by the connections 24 from power distribution module 22 so that some or all of the electrodes 28 are electrically connected to electrical conductors 48 a and 48 b .
  • alternating electrodes may be connected to opposite power polarities, in others some electrodes may not be directly connected to the power supply but instead become electrically activated by the ionic currents in the liquids being treated, resulting in each side of such intermediate electrodes having opposite polarities.
  • Conductors 48 a and 48 b are connected to a switching unit 50 contained in the control unit 26 that may alternate the electrical polarity of alternate electrodes 28 .
  • the switch is depicted logically as a double pole, triple throw electrical switch and will be typically implemented by solid-state electronics controllable by control line 51 .
  • One pole connects to a positive voltage line 52 from a voltage controllable DC power supply 58 and the other pole connects to a negative voltage line 53 from the voltage controllable DC power supply 58 .
  • the voltage controllable DC power supply 58 receives power from electrical mains 62 .
  • the throws of the switching unit 50 are controllable so that one conductor 48 a or 48 b may be connected to a given voltage (positive or negative) while the other conductor 48 a or 48 b is connected to the opposite voltage.
  • the positive voltage line 52 may connect to a current sensor 54 and voltage sensing point 56 , both of which are connected to inputs of a controller 60 , the latter being a special-purpose computer, for example, a programmable logic controller executing a stored program to control of the process as will be described.
  • a similar current sensor 54 and voltage sensing point 56 (not shown) may be provided on negative voltage line 53 .
  • Sensors 54 and 56 may also be built into the power supply 58 .
  • the programmable controller 60 also receives signals from the chemical sensors 40 and flow sensor 42 and may provide control signals to the pump 44 and valve 46 .
  • the controller 60 communicates with the touchscreen 27 or alternative user input device which may be a keyboard or other means known in the art.
  • the controller 60 includes a processor 70 and a control program 72 , the latter contained in the memory 81 communicating with the processor 70 as is generally understood in the art.
  • the program 72 will read various parameters of the process including the electrode current from current sensors 54 , the electrode voltage from voltage sensing points 56 , user entered parameters through touchscreen 27 , chemical environment sensing from the chemical sensors 40 , and/or the flow rate from the flow sensor 42 , and will provide output signals on control line 51 controlling the switching unit 50 and the power supply 58 .
  • output signals controlling the pump 44 and valve 46 and providing information on the touchscreen 27 may be provided.
  • Pump 44 or the valve 46 may be used as the flow controller, Pump 44 may be a variable speed pump and valve 46 may be a continuously adjustable valve.
  • the present inventors have determined that the quality of disinfection 82 of the liquid (for example, measured by log kills of test bacteria) peaks when the period between polarity reversals is approximately 17 seconds (0.03 Hz) in duration for high performance duplex stainless steel electrodes 28 .
  • the disinfection falls off rapidly when the period between polarity reversals is less than 5 seconds (0.01 Hz) or greater than 50 seconds (0.1 Hz). This measurement was produced on a laboratory scale in a 12 mL cell volume with electrodes spaced 1 cm apart, and a flow rate of 750 mL/min in replicated experiments.
  • FIG. 4 the diagram illustrates one configuration of a system to disinfect cold food processing liquids.
  • Housing 400 contains liquid outlets or spray nozzles 414 through which a cooling liquid 404 , normally salt brine or water, flows to impinge on food products (not shown) to cool them down from a higher temperature to a lower one for further processing or storage.
  • a main flow stream 406 is drawn from the sump 402 at the bottom of this chamber and provides a source of cooling liquid 404 which may flow through a pump 408 and a strainer 410 to filter out larger particles and a heat exchanger 412 which chills the liquid prior to discharge through the liquid outlets 414 .
  • a side stream 416 is taken from the sump 402 through a pump 418 and strainer 420 to the electrolytic cell 422 where treatment occurs and is then discharged back to the sump 402 .
  • this flow may be a side stream of the main flow stream 406 taken after strainer 410 eliminating the need for a second pump 418 and strainer 420 but removing the capability of operating these two liquid circuits independently.
  • Makeup liquid 424 is added as required to keep the sump full.
  • FIG. 5 the diagram illustrates one configuration of a system to chill solid food products with a liquid, normally water, that is disinfected by the invention disclosed herein.
  • a water tank 500 containing water 502 a conveying means 504 for moving products from one end to the other receives food products 506 , such as recently slaughtered and eviscerated poultry which are then conveyed through the water 502 .
  • Chilled product is removed by unloading means 508 .
  • Makeup water 510 replaces water lost due to carry-off on the product and additional flow may be provided to freshen the water, which then overflows to drain 512 .
  • a pump 514 connected with the water tank 500 propels a stream of water 516 into a rechiller 518 which removes heat from the water stream exits back into the chiller tank 500 .
  • Flow control valve 520 redirects some or all of the water stream 522 through the electrode cell 524 where electrolytic disinfection takes place.
  • the side stream 526 exits the electrode cell 524 and is recombined with the main rechiller water stream 516 to go through the rechiller 518 and back to the water tank 500 .
  • this block diagram represents a flume water system designed to wash food products such as vegetables and fruits.
  • Product to be treated 600 enters the flume 602 where washing and conveying water 604 moves the product under the shower header 608 where shower water 606 is distributed. Washed product exits the flume 610 and enters a strainer 612 , oftentimes a shaking one, and the drained product 614 is transported for further processing or packaging.
  • the drain water enters a fine strainer 616 where smaller solids and impurities are removed via outlet 618 .
  • a pump 620 propels the drained water through a flow control valve 622 a rechiller 624 and then back into the flume 602 or shower header 608 .
  • Flow control valve 622 redirects some or all of the strainer water 626 through the electrode cell 628 for disinfection with the discharge water 630 being blended back into the main flow.
  • this graph shows the percentage removal 700 of a pharmaceutical, the estrogen 17-alpha-ethinylestradiol, using the disclosed electrochemical treatment process with the treatment fluid being final wastewater effluent with pharmaceutical and personal care product residuals at their normal levels for such liquids.
  • the graph compares this with disinfection efficacy 702 achieved during each test number, with these tests being conducted at varying power levels and treatment times.
  • the tests show the high pharmaceutical removal efficacy of the process even when operated to achieve relatively low disinfection levels. There is a strong correlation between contaminant destruction 700 and disinfection efficacy 702 .
  • this graph shows the percentage removal 800 of a personal care product residual, the antibiotic triclosan, using the disclosed electrochemical treatment process with the treatment fluid being final wastewater effluent with pharmaceutical and personal care product residuals at their normal levels for such liquids.
  • the graph compares this with disinfection efficacy 802 achieved during each test number, with these tests being conducted at varying power levels and treatment times.
  • the tests show the high pharmaceutical removal efficacy of the process even when operated to achieve relatively low disinfection levels.
  • the present inventors have discovered that for the electrochemical method of this patent, that disinfection efficacy, a low cost, easily measured value, serves as a robust surrogate for the efficacy of removal of trace pharmaceuticals and personal care product residuals.
  • the inventors have determined that for liquid streams without significant bacterial load, a safe, food grade bacteria like Lactobacillus Acidophilus , used to make yoghurt, can be added to the liquid to provide this surrogate disinfection measure. This is an inexpensive alternative to the expensive, time-consuming, analysis required to measure trace pharmaceuticals and personal care product oxidation performance.
  • electrode 28 a may be a conductive tube or rod surrounded by a concentric conductive tube electrode 28 b wherein an annular space is created for passage of the liquid being treated 34 and 35 .

Abstract

An electrolytic method and apparatus for treating liquids using a flow cell with widely spaced electrodes and polarity reversing power designed to prevent electrode fouling and provide for long continuous liquid treatment running times.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims the benefit of U.S. Provisional Application 61/248,077 filed Oct. 2, 2009 hereby incorporated by reference.
  • BACKGROUND OF THE INVENTION
  • The present invention relates to an apparatus for treating liquids to disinfect and oxidize contaminants and in particular to a method and apparatus of this type using frequent polarity reversal of the power applied to the electrodes.
  • Liquids, including water and solvent based ones, are capable of being treated by many different methods known the in art. Biological methods can disinfect and oxidize, but require long treatment times, a large equipment footprint and other complications. Such methods are commonly used to treat municipal wastewater but have had limited application in liquid treatment at the industrial scale.
  • The treatment of liquid streams through the addition of disinfecting chemicals such as chlorine or bromine is also well-known. The class of chlorine disinfectants includes chlorine gas, hypochlorous acid, sodium hypochlorite, and chlorine dioxide. These chemicals typically are purchased in bulk, with attendant cost, storage and dosing issues. Chlorine gas has significant safety and security issues associated with it.
  • Chlorine is often used because of its low cost. But in some applications, for example in chiller water, cold brine and flume water used in poultry, meat and vegetable processing, the addition of these chemicals may be disfavored because of concerns about the generation of off-taste in the product and chemical byproducts that may adversely affect product quality, plant personnel or the environment. Chlorine's efficacy is also dramatically affected by pH levels, oftentimes requiring additional pH adjustment that adds to cost and operating complications. As another disadvantage, chlorine dosage requirements in some applications can be very high due to high organic loads and pathogen levels. High dosages of these chemicals make the process difficult to control to maintain reliable disinfection without generating excessive unwanted chlorinated byproducts, such as trichloramines. They also make it difficult to maintain residual chlorine levels within the levels that may be permitted by the United States Department of Agriculture (USDA) or other application-specific regulations.
  • Other chemicals such as hydrogen peroxide and peracetic acid are used as disinfectants but typically have high cost and other issues associated with them.
  • High temperature pasteurization can be used for disinfection but requires high energy use and post-treatment cooling. Ultraviolet light is sometimes used for water and wastewater final effluent disinfection. A significant drawback to ultraviolet systems is their inability to work in turbid liquids with suspended solids or color.
  • It also is known that electrical methods can be used to disinfect liquids. Electroporation is a high voltage, low current process that disinfects by penetrating the cell walls of pathogens and either destroying or inactivating them. Electroporation has many laboratory scale uses, including for the insertion of genes in cells, but has not scaled up well to industrial use due to the high voltages used and other reasons.
  • Research has also been done on disinfection at various alternating current frequencies, including those in the low kilohertz to microwave range. However, it has been shown that the primary method of disinfection at these frequencies comes through the heating of liquid to low pasteurization temperatures, an energy inefficient process.
  • Direct current electrolytic processes have also been demonstrated to disinfect contaminants in liquids. In electrolysis, comparatively low voltage, high current electrical power is passed through the liquid, breaking bonds in chemical compounds and causing destructive changes to biological cells. Depending on the application, this can be a more energy efficient method.
  • Electrolytic systems called hypochlorite generators have been used commercially for indirect disinfection of liquids. Electrodes are immersed in a relatively pure salt water solution and direct current is applied to generate hypochlorite. The hypochlorite-enhanced solution is then injected into the liquid stream to be treated. Such systems typically use different anode and cathode materials. They have the same issues with pH control as with the direct addition of hypochlorite.
  • Another electrolytic method uses an ion exchange membrane in a salt solution between direct current electrodes to create separate acidic anolyte and alkaline catholyte solutions with purported electrochemically activated properties. Sometimes these two liquids are used separately for cleaning, or sometimes may be combined and marketed under rather fanciful names implying health and longevity effects.
  • Another electrolytic process is used to directly treat swimming pool water to which salt is added. Since swimming pool liquid is less controlled regarding contaminants, the polarity is reversed on the electrodes, typically every few hours, to reduce electrode fouling caused by the electrochemical deposition of materials onto the electrodes.
  • These electrolytic systems use plate or expanded metal electrodes that typically are spaced 0.5-2 mm apart. Any polarity reversal is done only very infrequently, typically 2-6 hours between reversals. The anodes typically use one or more metal oxides from the platinum group metals as a coating over a valve metal such as titanium. It has generally been observed that polarity reversing power is highly destructive to these coatings with various mechanisms of failure being described including hydrogen embrittlement when the electrode is operated as a cathode.
  • Lab scale research has been done with electrolytic systems, typically with static treatment cells or very low volume flow cells, to demonstrate disinfection and also the oxidation of trace levels of contaminants such as endocrine disruptors in water and wastewater. This research generally has been done with liquids containing low chemical oxygen demand (COD) and biological oxygen demand (BOD) loads, an unrealistic situation for many industrial liquid treatment applications. Some of this research has used conventional metals like 300 series stainless steel for their electrodes. These test results are not relevant to industrial applications where the liquid flowing through a treatment cell may have significant COD and BOD loads, with these loads being continuously replaced by a new influx of organic and inorganic contaminants. In addition, these tests typically have not analyzed the treated solution for an increase in dissolved heavy metal ions. Under such electrolytic treatment, these heavy metal concentrations can quickly rise to levels above those permitted by the EPA, USDA, FDA or other relevant regulatory agency.
  • SUMMARY OF THE INVENTION
  • The present invention provides direct, high flow rate, electrical treatment of liquids with significant organic loads and suspended solids, including but not limited to poultry chiller water and processed meats chiller brine. While the inventors do not wish to be bound by a particular theory, it is believed that such direct treatment may provide significant advantages in exposing the water to short-lived chemical species. The possibility of such direct treatment required a determination that treatment effectivity could be maintained for relatively large electrode gaps (5 mm or larger) and without debilitating electrodes fouling, both empirically confirmed by the present inventors.
  • Specifically then, the present invention provides a liquid treatment system with a first and second electrode having a comparatively large separation between them that permits the passage of a significantly large volume of liquid that may contain small solids. A polarity reversing power supply is connected across the first and second electrodes, the power supply switching the polarity of the voltage at a period determined empirically for each liquid being treated within a specified range.
  • The inventors have determined that there is an optimum narrow frequency range around 0.03 Hz for high performance duplex stainless steel electrodes above or below which a substantial reduction of treatment performance occurs for a particular liquid stream. This equates to a polarity reversal approximately every 17 seconds. In addition, the disinfection falls off rapidly when the period between polarity reversals is less than 5 seconds (0.1 Hz) or greater than 50 seconds (0.01 Hz).
  • In addition, the inventors have determined that for catalytic platinum group metal electrodes, the detrimental effects of frequent polarity reversal on electrode life can be balanced against the need to change polarities to prevent electrode fouling and that the optimal time between polarity reversals is approximately between 10 seconds and 60 minutes, depending on the composition of the liquid stream.
  • It is thus a feature of at least one embodiment of the invention to maximize treatment efficacy while balancing electrode lifetimes by performing a polarity reversal in the range of approximately 10 seconds to 60 minutes.
  • Laboratory research results with electrochemical treatment of liquids has heretofor been difficult or impossible to scale up to commercially useful liquid treatment due to the need to separate out any solids plus organic or inorganic load that could physically plug the electrodes with their narrow spacing or otherwise cause fouling. Separation processes are capital intensive, require regular cleaning and maintenance, and are not warranted or desirable in many applications.
  • It is thus a feature of at least one embodiment of the invention to space the electrodes greater than 5 mm apart.
  • In electrochemistry things that work at the lab scale with closely spaced electrodes, low flow rates, and very short running times typically cannot be duplicated even at low commercial flow rates treating liquids with varying composition and with a necessarily wider gap between the electrodes to provide the required higher flow rates, acceptable pressure drops and to permit passage of small solids. The inventors have successfully treated very challenging liquid streams at flow rates up to 650 gallons per minute.
  • It is thus a feature of at least one embodiment of this invention to treat flow rates of five gallons per minute and higher.
  • The inventors have also found that electrolysis degrades many metals and their oxides when used for electrolysis. Very high levels of metal ions, such as chromium, nickel, iron, and tin are found in liquids that have been treated with electrode materials containing them. This prevents conventional electrolysis with such electrodes from being used in applications where metal toxicity is a concern. They remain quite appropriate for various other treatment applications, such as electrowinning and electro-flocculation. The inventors have also found that catalytic electrodes, for example those from the platinum group metals and metal oxides, do not dissolve into the liquid under polarity reversing electrolysis to any measurable extent.
  • It is thus a feature of at least one embodiment of the invention to use catalytic electrode surfaces including those from the platinum group metals and metal oxides, and from the doped diamond category.
  • It is known in the art that various catalytic metals and metal oxides in liquids containing water and salt generate differing proportions of reactive oxygen species and/or chlorine species that may be useful for liquid treatment, such as disinfection and oxidation. For example, under electrolysis, ruthenium oxide is known to generate a high proportion of chlorine species and fewer reactive oxygen species when used as an anode. Boron doped diamond is known to produce a much higher ratio of reactive oxygen species when used as an anode.
  • It is thus a feature of at least one embodiment of the invention to provide electrode pairs of opposite polarity with surfaces of different metals or metal oxides. Polarity reversal can be controlled to provide different times between polarity reversal for each specific electrode surface, enabling the control system to tailor the reactive species being generated to meet the needs of a particular liquid stream being treated.
  • Lab scale testing has typically been done on liquids where such contaminants that affect process performance, like organic loads and bacteria levels are not replaced during the test cycle, further contributing to the inability to extrapolate test results to commercial reality.
  • It is thus a feature of at least one embodiment of this invention to treat liquids that have a chemical oxygen demand of 200 mg/l or higher with a continuing influx of organic and inorganic loads.
  • In many commercial applications, for example the disinfection of processed meats chilling brine, a fluid is continuously recirculated at high flow rates for another purpose, such as cooling a product and rechilling the liquid to maintain its desired temperature. The inventors have shown that in many cases a proportionally smaller liquid flow is all that is required to maintain the desired level of treatment in the liquid, reducing the size of the electrolytic treatment cell, associated piping and other components.
  • It is thus a feature of at least one embodiment of this invention to treat a side stream or smaller volume of a main flow.
  • In certain commercial applications the liquid stream is directly discharged and is not recycled for another reason. In such situations the desired treatment level may be difficult to achieve at reasonable equipment cost in a single pass. The inventors have determined that recycling a portion of the treated liquid back to the treatment cell can have a synergistic effect on process efficacy.
  • It is thus a feature of at least one embodiment of this invention to directly treat a liquid stream on a one-pass basis, but to recycle a portion of this liquid back through the treatment cell to obtain the overall treatment efficacy desired.
  • Methods for disinfecting example food processing liquid streams are disclosed.
  • It is thus a feature of at least one embodiment of this invention to disinfect food processing liquids.
  • A method for oxidizing and destroying trace pharmaceuticals and personal care products is disclosed.
  • It is thus a feature of at least one embodiment of this invention to provide a method to remove pharmaceutical and personal care product (PPCP) residuals from a liquid stream.
  • In addition, the inventors have found that disinfection efficacy, a low cost, easily measured value, serves as a robust surrogate for the efficacy of removal of trace pharmaceuticals and personal care product residuals.
  • It is thus a feature of at least one embodiment of this invention to use the results from tests for disinfection efficacy as a practical means to estimate the efficacy of PPCP residual oxidation.
  • In addition, the inventors have determined that for liquid streams without significant bacterial load, a safe, food grade bacteria like Lactobacillus Acidophilus, used to make yogurt, can be added to the liquid to provide this surrogate disinfection measure.
  • It is thus a feature of at least one embodiment of this invention to add bacteria to a liquid stream and use the results of tests for disinfection efficacy of this bacteria as a practical means to estimate the efficacy of PPCP residual oxidation.
  • This electrochemical process produces oxygen at the anode and hydrogen at the cathode. With the polarity reversal of this process, each electrode in a pair alternates between generating hydrogen and oxygen.
  • It is thus a feature of at least one embodiment of this invention to generate hydrogen and oxygen both as a mixed species and as separate elements, the latter achieved by an external separation means such as a selective membrane.
  • These particular objects and advantages may apply to only some embodiments falling within the claims and thus do not define the scope of the invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a perspective view of a liquid treatment system in one embodiment of the present invention showing a main housing holding opposed planar electrodes between liquid inlets and outlets, a power distribution module, and a control unit;
  • FIG. 2 is a detailed block diagram of the components of FIG. 1 showing the electrodes as flat plates;
  • FIGS. 3 a and 3 b are graphs of disinfection versus frequency showing a preferred range of operation of the present invention for stainless steel and catalytic electrodes;
  • FIG. 4 is a simplified representation of a method to disinfect processed meat and processed poultry products immediately after a cooking cycle to rapidly cool them for further processing, packaging or storage;
  • FIG. 5 is a simplified representation of a method to disinfect raw poultry chiller water to rapidly cool the birds for further processing, packaging or storage;
  • FIG. 6 is a simplified representation of a method to disinfect water used to wash and chill vegetables and fruits, such as cut leafy greens, to help ensure the safety of the product and permit extended reuse of the water;
  • FIG. 7 is a graph of performance achieved with the method of the patent for removing trace pharmaceuticals from wastewater showing the strong correlation of trace pharmaceutical destruction with bacterial disinfection performance on this same liquid;
  • FIG. 8 is a graph of performance achieved with the method of the patent for removing trace personal care product residuals from wastewater showing the strong correlation of trace personal care product destruction with bacterial disinfection performance on this same liquid; and
  • FIG. 9 is a simplified representation of an alternate electrode arrangement using a rod and cylinder configuration;
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
  • Referring now to FIGS. 1 and 2, a liquid treatment system 10 per the present invention may include a treatment unit 12 providing a liquid inlet 14 and outlet 16 to conduct liquid across internal electrodes 28. The electrodes 28 are contained in an insulating housing 18 supported on frame 20. A power distribution module 22 provides electrical connections 24 to the internally contained electrodes 28 for power received from a control unit 26. The control unit 26 has a touchscreen user interface 27 for the display and entry of data including critical operation parameters.
  • Referring now to FIG. 2, the treatment unit 12 includes two or more generally planar and parallel electrodes 28 held in a channel 36 between the inlet 14 and the outlet 16. The electrodes 28 are separated along an axis 30 generally perpendicular to the flow of liquid by gaps 32 to receive the influent liquid 34 therethrough. The separation of the electrodes 28 will be greater than 5 mm to permit the passage of influent liquid 34 without undue risk of clogging.
  • One or more chemical sensors 40 may be positioned in sensor fitting 38 downstream from the electrodes 28 and channel 36 to measure chemical properties of the liquid and/or a flow sensor 42 may be positioned in the influent liquid 34 or effluent liquid 35 to measure the flow across the electrodes 28. The chemical sensors 40 may include those measuring pH, oxidation-reduction potential, chlorine level, free chlorine level, or total chlorine level.
  • The amount of flow through the channel 36 may be controlled by an electrically driven pump 44 and/or valve 46 alone or in combination.
  • The electrodes 28 are electrically isolated from each other as held by the housing 18 but may be joined by the connections 24 from power distribution module 22 so that some or all of the electrodes 28 are electrically connected to electrical conductors 48 a and 48 b. In some configurations alternating electrodes may be connected to opposite power polarities, in others some electrodes may not be directly connected to the power supply but instead become electrically activated by the ionic currents in the liquids being treated, resulting in each side of such intermediate electrodes having opposite polarities.
  • Conductors 48 a and 48 b are connected to a switching unit 50 contained in the control unit 26 that may alternate the electrical polarity of alternate electrodes 28. The switch is depicted logically as a double pole, triple throw electrical switch and will be typically implemented by solid-state electronics controllable by control line 51. One pole connects to a positive voltage line 52 from a voltage controllable DC power supply 58 and the other pole connects to a negative voltage line 53 from the voltage controllable DC power supply 58. The voltage controllable DC power supply 58 receives power from electrical mains 62.
  • The throws of the switching unit 50 are controllable so that one conductor 48 a or 48 b may be connected to a given voltage (positive or negative) while the other conductor 48 a or 48 b is connected to the opposite voltage.
  • The positive voltage line 52 may connect to a current sensor 54 and voltage sensing point 56, both of which are connected to inputs of a controller 60, the latter being a special-purpose computer, for example, a programmable logic controller executing a stored program to control of the process as will be described. A similar current sensor 54 and voltage sensing point 56 (not shown) may be provided on negative voltage line 53. Sensors 54 and 56 may also be built into the power supply 58. The programmable controller 60 also receives signals from the chemical sensors 40 and flow sensor 42 and may provide control signals to the pump 44 and valve 46. In addition, the controller 60 communicates with the touchscreen 27 or alternative user input device which may be a keyboard or other means known in the art.
  • The controller 60 includes a processor 70 and a control program 72, the latter contained in the memory 81 communicating with the processor 70 as is generally understood in the art. In operation, the program 72 will read various parameters of the process including the electrode current from current sensors 54, the electrode voltage from voltage sensing points 56, user entered parameters through touchscreen 27, chemical environment sensing from the chemical sensors 40, and/or the flow rate from the flow sensor 42, and will provide output signals on control line 51 controlling the switching unit 50 and the power supply 58. In addition, output signals controlling the pump 44 and valve 46 and providing information on the touchscreen 27 may be provided.
  • Pump 44 or the valve 46 may be used as the flow controller, Pump 44 may be a variable speed pump and valve 46 may be a continuously adjustable valve.
  • Referring now to FIG. 3 a, the present inventors have determined that the quality of disinfection 82 of the liquid (for example, measured by log kills of test bacteria) peaks when the period between polarity reversals is approximately 17 seconds (0.03 Hz) in duration for high performance duplex stainless steel electrodes 28. In addition, the disinfection falls off rapidly when the period between polarity reversals is less than 5 seconds (0.01 Hz) or greater than 50 seconds (0.1 Hz). This measurement was produced on a laboratory scale in a 12 mL cell volume with electrodes spaced 1 cm apart, and a flow rate of 750 mL/min in replicated experiments.
  • Referring now to FIG. 3 b, for platinum-group catalytic electrodes 28 the performance peak appears to be occur the closer the electrodes approach direct current. This measurement does not consider the counteracting issues of electrode fouling due to organic and inorganic loads, which occur the closer the electrodes are run to pure unswitched direct current. In commercial scale operations with organic and inorganic loads of 200 mg/l and more of measured chemical oxygen demand, the inventors have shown that disinfection performance degrades and electrode fouling occurs when the time between current reversals exceeds 60 minutes and at even shorter current reversal periods for very high organic and inorganic loads.
  • Referring now to FIG. 4, the diagram illustrates one configuration of a system to disinfect cold food processing liquids. Housing 400 contains liquid outlets or spray nozzles 414 through which a cooling liquid 404, normally salt brine or water, flows to impinge on food products (not shown) to cool them down from a higher temperature to a lower one for further processing or storage. A main flow stream 406 is drawn from the sump 402 at the bottom of this chamber and provides a source of cooling liquid 404 which may flow through a pump 408 and a strainer 410 to filter out larger particles and a heat exchanger 412 which chills the liquid prior to discharge through the liquid outlets 414.
  • A side stream 416 is taken from the sump 402 through a pump 418 and strainer 420 to the electrolytic cell 422 where treatment occurs and is then discharged back to the sump 402. Alternatively, this flow may be a side stream of the main flow stream 406 taken after strainer 410 eliminating the need for a second pump 418 and strainer 420 but removing the capability of operating these two liquid circuits independently. Makeup liquid 424 is added as required to keep the sump full.
  • Referring now to FIG. 5, the diagram illustrates one configuration of a system to chill solid food products with a liquid, normally water, that is disinfected by the invention disclosed herein. A water tank 500 containing water 502 a conveying means 504 for moving products from one end to the other receives food products 506, such as recently slaughtered and eviscerated poultry which are then conveyed through the water 502. Chilled product is removed by unloading means 508. Makeup water 510 replaces water lost due to carry-off on the product and additional flow may be provided to freshen the water, which then overflows to drain 512.
  • Temperature rises in the water 502 due to the heat removed from the food product. A pump 514 connected with the water tank 500 propels a stream of water 516 into a rechiller 518 which removes heat from the water stream exits back into the chiller tank 500. Flow control valve 520 redirects some or all of the water stream 522 through the electrode cell 524 where electrolytic disinfection takes place. The side stream 526 exits the electrode cell 524 and is recombined with the main rechiller water stream 516 to go through the rechiller 518 and back to the water tank 500.
  • Referring now to FIG. 6, this block diagram represents a flume water system designed to wash food products such as vegetables and fruits. Product to be treated 600 enters the flume 602 where washing and conveying water 604 moves the product under the shower header 608 where shower water 606 is distributed. Washed product exits the flume 610 and enters a strainer 612, oftentimes a shaking one, and the drained product 614 is transported for further processing or packaging.
  • The drain water enters a fine strainer 616 where smaller solids and impurities are removed via outlet 618. A pump 620 propels the drained water through a flow control valve 622 a rechiller 624 and then back into the flume 602 or shower header 608.
  • Flow control valve 622 redirects some or all of the strainer water 626 through the electrode cell 628 for disinfection with the discharge water 630 being blended back into the main flow.
  • Referring now to FIG. 7, this graph shows the percentage removal 700 of a pharmaceutical, the estrogen 17-alpha-ethinylestradiol, using the disclosed electrochemical treatment process with the treatment fluid being final wastewater effluent with pharmaceutical and personal care product residuals at their normal levels for such liquids. The graph compares this with disinfection efficacy 702 achieved during each test number, with these tests being conducted at varying power levels and treatment times. The tests show the high pharmaceutical removal efficacy of the process even when operated to achieve relatively low disinfection levels. There is a strong correlation between contaminant destruction 700 and disinfection efficacy 702.
  • Referring now to FIG. 8, this graph shows the percentage removal 800 of a personal care product residual, the antibiotic triclosan, using the disclosed electrochemical treatment process with the treatment fluid being final wastewater effluent with pharmaceutical and personal care product residuals at their normal levels for such liquids. The graph compares this with disinfection efficacy 802 achieved during each test number, with these tests being conducted at varying power levels and treatment times. The tests show the high pharmaceutical removal efficacy of the process even when operated to achieve relatively low disinfection levels. There is a strong correlation between contaminant destruction 800 and disinfection efficacy 802.
  • Referring now to FIGS. 7 and 8, the present inventors have discovered that for the electrochemical method of this patent, that disinfection efficacy, a low cost, easily measured value, serves as a robust surrogate for the efficacy of removal of trace pharmaceuticals and personal care product residuals. In addition, the inventors have determined that for liquid streams without significant bacterial load, a safe, food grade bacteria like Lactobacillus Acidophilus, used to make yoghurt, can be added to the liquid to provide this surrogate disinfection measure. This is an inexpensive alternative to the expensive, time-consuming, analysis required to measure trace pharmaceuticals and personal care product oxidation performance.
  • Referring now to FIG. 9, in an alternate configuration electrode 28 a may be a conductive tube or rod surrounded by a concentric conductive tube electrode 28 b wherein an annular space is created for passage of the liquid being treated 34 and 35.
  • The present invention has been described in terms of the preferred embodiment, and it is recognized that equivalents, alternatives, and modifications, aside from those expressly stated, are possible and within the scope of the appending claims.

Claims (24)

1. A liquid treatment system comprising:
a treatment cell receiving a liquid to be treated at a rate of at least 5 gallons per minute;
at least a first and a second electrode positioned within the treatment cell and having a separation of no less than 5 mm permitting the liquid with suspended solids or an organic load to pass therebetween wherein at least one of the electrodes has a surface selected from the group consisting of metals, metal oxides and doped diamond;
a polarity reversing power supply connected across the at least two electrodes, the power supply providing an alternating positive and negative electrical power; and
a power supply controller communicating with the polarity reversing power supply to provide a polarity reversal of the electrical power to the at least two electrodes during a cycle period having a length of at least 10 seconds and no more than 60 minutes.
2. The liquid treatment system of claim 1 wherein the electrodes are opposed substantially planar conductive plates.
3. The liquid treatment system of claim 1 wherein the at least two electrodes are a substantially concentric tube and center electrode.
4. The liquid treatment system of claim 1 wherein the at least two electrodes have a surface containing at least one platinum group metal consisting of platinum, palladium, rhodium, iridium, osmium, and ruthenium.
5. The liquid treatment system of claim 1 wherein one of the at least two electrodes has a different surface material composition than the other of the at least two electrodes.
6. The liquid treatment system of claim 1 wherein the cycle period provides different durations of negative and positive electrical power.
7. The liquid treatment system of claim 1 wherein the cycle period provides substantially equal durations of negative and positive power.
8. The liquid treatment system of claim 1 wherein the liquid being treated has a chemical oxygen demand of at least 200 mg/l.
9. The liquid treatment system of claim 1 wherein a flow splitting means delivers a side stream of a circulating liquid to the treatment cell, which side stream after treatment is then blended back into the circulating liquid after treatment.
10. A method of treating a liquid with suspended solids or organic load comprising the steps of:
passing the liquid through a treatment cell containing at least a first and second electrode positioned within the treatment cell and having a separation of no less than 5 mm, wherein one or more of the electrodes has surfaces selected from the group consisting of metals, metal oxides and doped diamond; wherein said liquid flows through the treatment cell at a rate of at least 5 gallons per minute;
applying power to the electrodes the power having an alternating negative and positive polarity during a cycle period having a length of at least 10 seconds and no more than 60 minutes.
11. The liquid treatment method of claim 10 wherein the at least first and second electrode have surfaces containing at least one platinum group metal consisting of platinum, palladium, rhodium, iridium, osmium, and ruthenium.
12. The liquid treatment method of claim 10 wherein at least one electrode has a different surface material composition than at least one other electrode.
13. The liquid treatment method of claim 10 wherein the cycle period provides different durations of negative and positive electrical power.
14. The liquid treatment method of claim 10 wherein the cycle period provides substantially equal durations of negative and positive power.
15. The liquid treatment method of claim 10 wherein the liquid being treated has a chemical oxygen demand of at least 200 mg/l.
16. The liquid treatment method of claim 10 wherein a side stream of a circulating liquid is treated and blended back into the circulating liquid.
17. The liquid treatment method of claim 10 wherein a portion of the treated liquid is circulated back into the liquid treatment system inlet.
18. The liquid treatment method of claim 10 wherein the treatment is disinfection of the liquid stream.
19. The liquid treatment method of claim 10 wherein the treatment is disinfection of materials selected from the group consisting of: food processing liquids, processed meat and poultry chiller brine or water, raw poultry processing chiller water, and fruit and vegetable processing flume water.
20. The liquid treatment method of claim 10 wherein the treatment oxidizes organic and inorganic contaminants of the liquid stream being treated.
21. The liquid treatment method of claim 20 wherein the treatment is a destruction of pharmaceutical and personal care product residuals.
22. The liquid treatment method of claim 10 including the step of monitoring a bacteria in the liquid and wherein a disinfection efficacy of bacteria in the liquid is used as a proxy for the efficacy of oxidation of trace residual chemicals.
23. The liquid treatment method of claim 22 including the steps of dosing the liquid with a known concentration of bacteria and testing results of killing of the bacteria to estimate the efficacy of oxidation of trace residual chemicals.
24. The liquid treatment method of claim 10 wherein the treatment is a generation of hydrogen and oxygen and separated by an external means.
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CA2776154A1 (en) 2011-04-07
US8961751B2 (en) 2015-02-24
WO2011041652A3 (en) 2011-06-30
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US20110079510A1 (en) 2011-04-07
CA2776176A1 (en) 2011-04-07

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