US20090229992A1 - Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators - Google Patents

Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators Download PDF

Info

Publication number
US20090229992A1
US20090229992A1 US12/473,744 US47374409A US2009229992A1 US 20090229992 A1 US20090229992 A1 US 20090229992A1 US 47374409 A US47374409 A US 47374409A US 2009229992 A1 US2009229992 A1 US 2009229992A1
Authority
US
United States
Prior art keywords
electrolytic cell
cleaning
current density
approximately
power supply
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
US12/473,744
Other languages
English (en)
Inventor
Justin Sanchez
Kevin Schwarz
Rodney E. Herrington
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.)
De Nora Miox Inc
Original Assignee
Miox Corp
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
Priority claimed from US11/946,772 external-priority patent/US7922890B2/en
Application filed by Miox Corp filed Critical Miox Corp
Priority to US12/473,744 priority Critical patent/US20090229992A1/en
Assigned to MIOX CORPORATION reassignment MIOX CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SANCHEZ, JUSTIN, HERRINGTON, RODNEY E., SCHWARZ, KEVIN
Publication of US20090229992A1 publication Critical patent/US20090229992A1/en
Priority to US13/198,276 priority patent/US20120048741A1/en
Priority to US14/154,579 priority patent/US20140124378A1/en
Assigned to UNION BAY CAPTIAL PARTNERS I, LLC reassignment UNION BAY CAPTIAL PARTNERS I, LLC SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MIOX CORPORATION
Priority to US15/064,385 priority patent/US10400349B2/en
Assigned to MIOX CORPORATION reassignment MIOX CORPORATION RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: UNION BAY CAPTIAL PARTNERS I, LLC
Priority to US16/526,144 priority patent/US11421337B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C02F1/4674—Treatment 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C02F2001/46119—Cleaning the 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
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • C02F2001/46185—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only anodic or acidic water, e.g. for oxidizing or sterilizing
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4613—Inversing polarity
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4614—Current
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46145—Fluid flow

Definitions

  • the present invention relates to an electrolytic on-site generator which is nearly free of maintenance.
  • Electrolytic technologies utilizing dimensionally stable anodes have been developed to produce mixed-oxidants and sodium hypochlorite solutions from a sodium chloride brine solution.
  • Dimensionally stable anodes are described in U.S. Pat. No. 3,234,110 to Beer, entitled “Electrode and Method of Making Same,” wherein a noble metal coating is applied over a titanium substrate.
  • Electrolytic cells have had wide use for the production of chlorine and mixed oxidants for the disinfection of water.
  • Some of the simplest electrolytic cells are described in U.S. Pat. No. 4,761,208, entitled “Electrolytic Method and Cell for Sterilizing Water”, and U.S. Pat. No. 5,316,740, entitled “Electrolytic Cell for Generating Sterilizing Solutions Having Increased Ozone Content.”
  • Electrolytic cells come in two varieties.
  • the first category comprises divided cells that utilize membranes to maintain complete separation of the anode and cathode products in the cells.
  • the second category comprises undivided cells that do not utilize membranes, but that also do not suffer nearly as much from issues associated with membrane fouling.
  • the source of these contaminants is typically either from the feed water to the on-site generation process or contaminants in the salt that is used to produce the brine solution feeding the system.
  • these unwanted films consist of manganese, calcium carbonate, or other unwanted substances.
  • the current accepted method of cleaning an electrolytic cell is to flush it with an acid (often muriatic or hydrochloric acid) to remove any deposits which have formed.
  • an acid often muriatic or hydrochloric acid
  • manufacturers recommend performing this action on a regular basis, at least yearly, but sometimes as often as on a monthly basis.
  • a more reliable method for insuring cleanliness of the electrolytic cell is to perform a cleaning process on an automated basis that does not require the use of a separate supply of consumables such as muriatic or hydrochloric acid, and that does not require operator intervention.
  • U.S. Pat. No. 5,853,562 to Eki, et al. entitled “Method and Apparatus for Electrolyzing Water” describes a process for reversing polarity on the electrodes in a membraneless electrolytic cell for the purpose of removing carbonate scale and extending the life of the electrolytic cell.
  • This method of electrolytic cell cleaning is routinely used in flow through electrolytic chlorinators that convert sodium chloride salt in swimming pool water to chlorine via electrolysis.
  • currently used flow through electrolytic cells are constructed of electrodes (anode and cathode) that both have common catalytic coatings. As electrical polarity is changed, the old cathode becomes the anode, and the anode becomes the cathode.
  • One of the other maintenance items for electrolytic generators is the requirement that operators occasionally measure and set water flow into the system.
  • the flow through the generator can vary greatly with incoming and outgoing water pressure and/or contaminant buildup in the system or electrolytic cells.
  • measurements are made with either flowmeters or with timed volume measurements, and adjustments to the flow are performed with manual valves. Keeping the electrolytic generator operating within flow specifications is important, as it ensures reliable long term operation the generator within its efficiency specifications.
  • the present invention is a method for operating an electrolytic cell, the method comprising the steps of supplying brine to an electrolytic cell, producing one or more oxidants in the electrolytic cell, detecting a level of contaminant buildup, automatically stopping the brine supply after an upper contaminant threshold is detected, automatically cleaning the electrolytic cell, thereby reducing contaminants in the electrolytic cell, and automatically continuing to produce the one or more oxidants after a lower contaminant threshold is detected.
  • the cleaning step preferably comprises providing brine to an acid generating electrolytic cell, generating an acid in the acid generating electrolytic cell, and introducing the acid into the electrolytic cell.
  • the acid preferably comprises muriatic acid or hydrochloric acid.
  • the method preferably further comprises the step of diluting the brine.
  • the detecting step preferably comprises utilizing a carbonate detector.
  • the detecting step preferably comprises measuring the rate of brine consumption in the electrolytic cell, optionally by measuring a quantity selected from the group consisting of flow meter output, temperature of the electrolytic cell, brine pump velocity, and incoming water flow rate.
  • the method preferably further comprises comparing the rate of brine consumption to the rate of brine consumption in a clean electrolytic cell.
  • the cleaning step optionally comprises using an ultrasonic device and/or using a magnetically actuated mechanical electrode cleaning device, or reversing the polarity of electrodes in the electrolytic cell, thereby lowering the pH at a cathode.
  • the present invention is also an apparatus for producing an oxidant, the apparatus comprising a brine supply, an electrolytic cell, an acid supply, and a control system for automatically introducing acid from the acid supply into the electrolytic cell.
  • the acid supply preferably comprises a second electrolytic cell, and the brine supply preferably provides brine to the second electrolytic cell during a cleaning cycle.
  • the apparatus preferably further comprises a variable speed brine pump, a carbonate detector, one or more thermowells for measuring a temperature of said electrolytic cell, and/or one or more flowmeters for measuring the brine flow rate.
  • the present invention is also an apparatus for producing an oxidant, the apparatus comprising a brine supply, an electrolytic cell, a cleaning mechanism in the electrolytic cell, and a control system for automatically activating the cleaning mechanism.
  • the cleaning mechanism preferably is selected from the group consisting of ultrasonic horn, magnetically actuated electrode mechanical cleaning device, and acidic solution at a cathode surface.
  • the apparatus preferably further comprises a device selected from the group consisting of a carbonate detector, at least one thermowell for measuring a temperature of said electrolytic cell, and a flowmeter for measuring a brine flow rate.
  • the present invention is also a method for cleaning an electrolytic cell comprising electrodes, the method comprising the steps of reversing polarities of two or more of the electrodes and providing a cleaning current density to the electrodes which is lower than an operational current density used during normal operation of the electrolytic cell.
  • the electrolytic cell preferably produces a concentration of free available chlorine greater than approximately four grams per liter, more preferably greater than approximately five grams per liter, and most preferably approximately eight grams per liter.
  • the operational current density is preferably greater than approximately one amp per square inch.
  • the cleaning current density is preferably less than approximately 20% of the operational current density, and more preferably between approximately 10% and approximately 15% of the operational current density.
  • the providing step is preferably performed for less than approximately thirty minutes, and more preferably for between approximately five minutes and approximately ten minutes.
  • the reversing step optionally comprises using at least one power supply relay or other switching device.
  • the operational current density is preferably provided by an operational power supply and the cleaning current density is preferably provided by a separate cleaning power supply.
  • the power producing capacity of the cleaning power supply is preferably smaller than the power producing capacity of the operational power supply.
  • the method preferably further comprises the step of monitoring a flow rate of electrolyte through the electrolytic cell.
  • the monitoring step is preferably performed using a flowmeter, a rotameter, or a pressure transducer, or monitoring a temperature difference across the electrolytic cell via a first thermocouple or thermowell disposed at an inlet of the electrolytic cell a second thermocouple or thermowell disposed at an outlet of the electrolytic cell.
  • the method preferably further comprises the step of automatically adjusting the flow rate, and preferably further comprises the step of initiating a cleaning cycle at a predetermined flow rate.
  • the present invention is also method for cleaning an electrolytic cell comprising electrodes, the method comprising the steps of reversing polarities of two or more of the electrodes and providing a cleaning voltage potential difference to the electrodes which is lower than an operational voltage potential difference used during normal operation of the electrolytic cell.
  • the electrolytic cell preferably produces a concentration of free available chlorine greater than approximately five grams per liter.
  • the providing step is preferably performed for a time between approximately five minutes and approximately ten minutes.
  • the reversing step preferably comprises using at least one power supply relay or other switching device.
  • the operational voltage potential difference is preferably provided by an operational power supply and the cleaning voltage potential difference is preferably provided by a separate cleaning power supply.
  • the method preferably further comprises the steps of monitoring a flow rate of electrolyte through the electrolytic cell and automatically adjusting the flow rate.
  • the present invention is also an apparatus for producing electrolytic products, the apparatus comprising an electrolytic cell comprising electrodes; a first power supply for providing a first current density to the electrodes, a second power supply for providing a second current density to the electrodes, the second power supply having an opposite polarity to the first power supply, wherein the second current density is smaller than the first current density.
  • the electrolytic cell preferably produces a concentration of free available chlorine greater than approximately five grams per liter.
  • the second current density is preferably between approximately 10% and approximately 15% of the first current density.
  • the apparatus preferably further comprises at least one power supply relay or other switching device, and preferably comprises a flow monitoring device for monitoring a flow rate of electrolyte through the electrolytic cell.
  • the flow monitoring device is preferably selected from the group consisting of a flowmeter, a rotameter, a pressure transducer, a pair of thermocouples, and a pair of thermowells. If a pair of thermocouples or thermowells is used, one thermocouple or thermowell is preferably disposed at an inlet of the electrolytic cell and another thermocouple or thermowell is preferably disposed at an outlet of the electrolytic cell.
  • the apparatus preferably further comprises an electronically operated valve for adjusting the flow rate.
  • FIG. 1 is a diagram of one embodiment of a low maintenance on-site generator unit.
  • FIG. 2 is a schematic of a reverse polarity system for electrolytic cell cleaning.
  • Embodiments of the present invention are methods and devices whereby an on-site generator electrolytic cell is preferably monitored automatically for buildup of contaminants on the electrode surfaces, and when those contaminants are detected, the electrolytic cell is cleaned automatically (i.e, without operator intervention), thereby providing a simple, low cost, and reliable process for achieving a highly reliable, low maintenance, on-site generator which does not require the typical operator intervention and/or auxiliary equipment (such as a water softener) now required for long life of electrolytic cells.
  • auxiliary equipment such as a water softener
  • the internal status of the electrolytic cells can be monitored automatically by monitoring cell inputs and performance. It is known that how much brine a cell consumes is dependent on the amount and type of film buildup on that given cell. If brine flow is continuously monitored, any dramatic change in brine flow to reach a given current at a given voltage is indicative of a potential problem with film buildup within a cell.
  • the invention preferably monitors the flow characteristics of the brine, incoming water, temperature, etc., to determine whether or not there has been contaminant buildup within the electrolytic cell. When potential film buildup is detected in the cell by the control system, the cell is preferably automatically acid washed.
  • a carbonate detector integrated with an electrolytic cell, automatic acid washing, and device controls may be utilized.
  • a separate electrolytic cell from the one used to create the mixed oxidant or sodium hypochlorite is preferably used to create the acid on site and on demand and to provide the acid for removing of contaminants in the electrolytic cell used for creating the sodium hypochlorite or mixed oxidants.
  • a reservoir is used to store concentrated acid onsite for cleaning the cell, and monitoring that acid reservoir and alarming operators when that acid reservoir would need to be refilled, as well as optionally diluting the acid to a desired concentration prior to washing the cell.
  • An ultrasonic cleaning methodology for automatically removing unwanted contaminants when the contaminants are detected by the methods described above may also be integrated into the present invention.
  • FIG. 1 An embodiment of the present invention is shown in FIG. 1 . All of the components of this device are preferably mounted to back plate 15 .
  • the controls and power supplies for all the separate components shown in this embodiment are all preferably contained within control box 5 , but may alternatively be located wherever it is convenient, preferably as long as there are master controls for the overall operation of the apparatus.
  • Control box 5 preferably shows the status of the unit via display 10 , and the master controls as well as electrical power and/or component signals are preferably carried via electrical connections 50 between control box 5 and the various individual components.
  • Water preferably enters the system through water entrance pipe 30 , and brine preferably enters the system through brine entrance pipe 25 .
  • Brine preferably stored in a saturated brine silo or tank, is preferably pumped via variable speed brine pump 20 , which is preferably controlled and powered by electrical connection 50 .
  • the brine then preferably passes through flow meter 35 , which can be electrically monitored via electrical connection 50 .
  • the control system can control the flow rate of the brine by increasing the speed of variable speed brine pump 20 .
  • control box 5 determines that flow is off target, for example in response to fluctuations in incoming pressure and/or flow to the electrolytic generator, it preferably automatically adjusts flow by changing electronically controlled cell inlet valve 6 . In this way, the cell can always operate near target flow levels and will not routinely require measurement or adjustment of incoming flows.
  • Data from any of the following sources is preferably used to determine the volumetric flow rate of brine: flow meter 35 , carbonate detector 60 , electrolytic cell 55 , acid generating electrolytic cell 45 , and/or thermowells 65 , 70 .
  • Valve 40 can direct flow either to electrolytic cell 55 or to acid generating electrolytic cell 45 .
  • Valve 40 typically flows an electrolyte comprising diluted brine (as both the concentrated brine and water inflows have preferably been plumbed together and the brine has been diluted before it reaches valve 40 ) to electrolytic cell 55 .
  • the system produces, for example, mixed oxidants or sodium hypochlorite.
  • carbonate detector 60 sends a series of signals to control box 5 , preferably via electrical connections 50 , which indicate whether or not a contaminant film is building up on electrolytic cell 55 .
  • control box 5 preferably begins an acid cleaning cycle in the device, wherein valve 40 is actuated via electrical connection 50 to force diluted brine through acid generating cell 45 , which is also preferably energized by control box 5 via electrical connections 50 .
  • the system preferably runs brine pump 20 to flow at a rate (as measured by flow meters 35 ) which has been optimized for optimal acid creation in acid generating electrolytic cell 45 .
  • the acid created in acid generation cell 45 preferably flows through electrolytic cell 55 , where it preferably cleans the contaminants, then flows through carbonate detector 60 .
  • the system preferably runs in this acid cleaning mode until carbonate detector 60 sends a signal to control box 5 indicating that the system is clean and can begin running again in standard mixed oxidant or sodium hypochlorite production mode.
  • the acid used to clean electrolytic cell 55 is preferably dumped to a separate waste drain after flowing through carbonate detector 60 instead of dumping it to the oxidant storage tank.
  • Electrolytic cell 55 may optionally be cleaned with an ultrasonic horn and/or a magnetically actuated electrode mechanical cleaning apparatus in addition to or in place of using an acid generating cell.
  • concentrated acid is stored in a reservoir.
  • control box 5 preferably activates a pump or valve to allow flow of the acid to electrolytic cell 55 .
  • the reservoir is preferably large enough to accommodate many different acid wash cycles. Some of that acid may potentially be diluted with standard incoming water to clean electrolytic cell 55 .
  • electrolytic cell 55 preferably may be cleaned on a predetermined cleaning schedule to ensure contaminants do not ruin electrolytic cell 55 .
  • this cleaning schedule would be based upon the number of hours that the electrolytic cell had been running since the last cleaning was completed, and is preferably frequent enough to ensure that there is no excessive contaminant buildup on the electrolytic cell.
  • the rate of brine consumption may optionally be used to determine the presence of contaminants in electrolytic cell 55 .
  • the rate of brine consumption is steady and measurable.
  • the carbonate layer acts as an electrical insulator between the anode and cathode within electrolytic cell 55 .
  • the rate of brine consumption increases to increase the conductivity within electrolytic cell 55 . This increased rate of brine consumption is compared to the normal rate of brine consumption.
  • Flow through electrolytic cell 55 can also be used to measure contaminant buildup within electrolytic cell 55 .
  • Flow can be measured indirectly by measuring the temperature rise through electrolytic cell 55 , for example by comparing the temperature difference between two thermocouples or inlet thermowell 65 and cell discharge thermowell 70 .
  • electrolytic cell 55 can be cleaned by any of the methods or components described above. Brine consumption may be measured using brine flow rate, tachometer rates of brine pump 20 , or incoming water flow rates.
  • the electrolytic cell may optionally be cleaned by reversing the polarity of the electrodes in electrolytic cell, while flowing electrolyte through the electrolytic cell or not, and preferably for a very short duration. Reversing the polarity of the electrodes, preferably at low current densities, lowers the pH at the cathode, which dissolves and removes the contaminants.
  • the dimensionally stable anode in the chlorine (4 to 8 gm/L) producing electrolytic cell described herein typically operates well at high current densities (up to 2 amps per square inch), but would fail quickly if polarity were reversed at the same current density.
  • a separate power source at lower current density and/or lower plate to plate voltages to clean the cell in reverse polarity mode, which is only operated when the normal chlorine production operational mode is in standby, so that the primary anode coating remains undamaged.
  • cleaning cycles of less than 30 minutes can be achieved, preferably ranging between approximately 5 minutes and 10 minutes.
  • Industry experience indicates that cell cleaning intervals of less than a week would represent an unfavorable situation where the feed water to the electrolytic cell, or the salt used to make the brine solution, would typically be poor quality. Intervals between cleaning of greater than one week are clearly the industry norm. Under the worst case condition of cleaning once per week, the loss of system duty cycle (production operation mode) would still be negligible.
  • both the anode and cathode surfaces of both primary and bi-polar electrodes are preferably coated with an appropriate dimensionally stable anode coating.
  • FIG. 2 is a schematic of an embodiment of a system for implementing reverse polarity cleaning.
  • Electrolytic cell 130 comprises anode 134 and cathode 132 with electrolyte flowing in at the bottom and oxidant flowing out at the top of the cell.
  • electrolytic cell 130 has electrical energy applied to anode 134 and cathode 132 via main power supply 136 .
  • electrolytic cell 130 will be cleaned by reversing the polarity on anode 134 and cathode 132 , effectively making anode 134 the cathode, and cathode 132 the anode.
  • the current density on anode 134 is preferably between approximately 1 and 2 amps per square inch. To avoid damage to anode 134 during the reverse polarity cleaning step, the current density is preferably less than approximately twenty percent of the normal operating current density range, and more preferably between about 10% and 15% of the normal operating current density range. Because the reverse polarity cleaning operation operates at much lower power settings, power is preferably supplied by cleaning power supply 138 , which can be much smaller than main power supply 136 . Power from main power supply 136 is transferred to electrolytic cell 130 preferably via main power cables 144 . Power from cleaning power supply 138 is transferred to electrolytic cell 130 preferably via cleaning power cables 146 .
  • the power supplies are preferably isolated via main power supply relay 140 and cleaning power supply relay 142 .
  • main power supply 136 In normal operation when chlorine is being produced within electrolytic cell 130 , main power supply 136 is energized and main power supply relay 140 is closed. To avoid backflow of current to cleaning power supply 138 with the wrong polarity, cleaning power supply relay 142 is open.
  • cleaning power supply relay 142 is open.
  • cleaning power supply 138 is energized
  • main power supply 136 is de-energized
  • main power supply relay 140 is open
  • cleaning power supply relay 142 is closed.
  • An alternative embodiment to the one shown in FIG. 2 uses the main power supply 136 to provide power for normal operation as well as the cleaning cycles.
  • This approach preferably employs the use of power supply relays 142 or other switching devices to reverse the polarity.
  • this approach requires the electrolytic cell brine concentrations during the cleaning cycle to be much less than in normal operation. With this approach, however, it is still preferable that the cleaning cycle be performed at lower current densities and/or lower potentials for short periods of time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Automation & Control Theory (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US12/473,744 2006-11-28 2009-05-28 Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators Abandoned US20090229992A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US12/473,744 US20090229992A1 (en) 2006-11-28 2009-05-28 Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators
US13/198,276 US20120048741A1 (en) 2006-11-28 2011-08-04 Electrolytic On-Site Generator
US14/154,579 US20140124378A1 (en) 2006-11-28 2014-01-14 Electrolytic On-Site Generator
US15/064,385 US10400349B2 (en) 2006-11-28 2016-03-08 Electrolytic on-site generator
US16/526,144 US11421337B2 (en) 2006-11-28 2019-07-30 Electrolytic on-site generator

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US86755706P 2006-11-28 2006-11-28
US11/946,772 US7922890B2 (en) 2006-11-28 2007-11-28 Low maintenance on-site generator
US5671808P 2008-05-28 2008-05-28
US12/473,744 US20090229992A1 (en) 2006-11-28 2009-05-28 Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US11/946,772 Continuation-In-Part US7922890B2 (en) 2006-11-28 2007-11-28 Low maintenance on-site generator

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/198,276 Continuation-In-Part US20120048741A1 (en) 2006-11-28 2011-08-04 Electrolytic On-Site Generator

Publications (1)

Publication Number Publication Date
US20090229992A1 true US20090229992A1 (en) 2009-09-17

Family

ID=41434648

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/473,744 Abandoned US20090229992A1 (en) 2006-11-28 2009-05-28 Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators

Country Status (6)

Country Link
US (1) US20090229992A1 (fr)
EP (1) EP2286003A4 (fr)
JP (1) JP2011522123A (fr)
CA (1) CA2763550A1 (fr)
MX (1) MX2010012917A (fr)
WO (1) WO2009155044A2 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080237054A1 (en) * 2006-11-28 2008-10-02 Miox Corporation Low Maintenance On-Site Generator
WO2012019016A3 (fr) * 2010-08-06 2012-05-31 Miox Corporation Générateur électrolytique embarqué
WO2012142435A2 (fr) * 2011-04-15 2012-10-18 Advanced Diamond Technologies, Inc. Système et procédé électrochimiques destinés à une génération sur site d'oxydants sous une densité de courant élevée
WO2012156671A2 (fr) 2011-05-17 2012-11-22 A-Zone Technologies Limited Cellule électrochimique et son procédé de fonctionnement
US20130193001A1 (en) * 2012-01-26 2013-08-01 Tennant Company Apparatus and Method for Generating Thermally-Enhanced Treatment Liquids
US20130199928A1 (en) * 2010-05-14 2013-08-08 Rico Reinders Device for producing an electrochemically activated solution by means of an electrolysis process
US8562810B2 (en) 2011-07-26 2013-10-22 Ecolab Usa Inc. On site generation of alkalinity boost for ware washing applications
US8882972B2 (en) 2011-07-19 2014-11-11 Ecolab Usa Inc Support of ion exchange membranes
US20150222116A1 (en) * 2014-02-04 2015-08-06 Jeffrey Allen Kaiser Control board for controlling channel sequencing of positive and negative dc voltage and current
EP2904689A4 (fr) * 2012-10-05 2016-02-10 Miox Corp Génération sur site sans transformateur
WO2019014467A1 (fr) * 2017-07-12 2019-01-17 Axine Water Technologies Inc. Mode de fonctionnement d'un système de traitement des eaux usées
US11027991B2 (en) 2017-10-05 2021-06-08 ElectroSea, LLC Electrolytic biocide generating system for use on-board a watercraft
ES2841509A1 (es) * 2019-12-16 2021-07-08 Santana Ramirez Alberto Andres Proceso para la limpieza de superficies catódicas en celdas voltaicas
US11345621B2 (en) 2019-02-11 2022-05-31 ElectroSea, LLC Self-treating electrolytic biocide generating system with recirculation
US11498855B2 (en) 2019-04-09 2022-11-15 ElectroSea, LLC Electrolytic biocide-generating unit

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013069164A1 (fr) * 2011-11-11 2013-05-16 Hosokawa Kanji Dispositif de production de gaz hho
KR102645213B1 (ko) * 2017-03-06 2024-03-07 에보쿠아 워터 테크놀로지스 엘엘씨 개선된 전기화학 시스템 설계를 위한 피드백 제어의 실행

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234110A (en) * 1959-02-06 1966-02-08 Amalgamated Curacao Patents Co Electrode and method of making same
US4087337A (en) * 1977-05-25 1978-05-02 Diamond Shamrock Corporation Rejuvenation of the efficiency of sea water electrolysis cells by periodic removal of anodic deposits
US4088550A (en) * 1977-05-25 1978-05-09 Diamond Shamrock Corporation Periodic removal of cathodic deposits by intermittent reversal of the polarity of the cathodes
US4479864A (en) * 1982-08-04 1984-10-30 The Japan Carlit Co., Ltd. Anode for electrolysis of seawater
USRE32077E (en) * 1977-06-30 1986-02-04 Oronzio Denora Impianti Elettrochimici S.P.A. Electrolytic cell with membrane and method of operation
US4710233A (en) * 1984-08-20 1987-12-01 Siemens Aktiengesellschaft Method and apparatus for cleaning, disinfecting and sterilizing medical instruments
US4761208A (en) * 1986-09-29 1988-08-02 Los Alamos Technical Associates, Inc. Electrolytic method and cell for sterilizing water
US4767511A (en) * 1987-03-18 1988-08-30 Aragon Pedro J Chlorination and pH control system
FR2644155A1 (fr) * 1989-03-07 1990-09-14 Levart Michel Appareil de sterilisation electrolytique des eaux
US5254226A (en) * 1992-05-05 1993-10-19 Ad Rem Manufacturing, Inc. Electrolytic cell assembly and process for production of bromine
US5316740A (en) * 1992-03-26 1994-05-31 Los Alamos Technical Associates, Inc. Electrolytic cell for generating sterilization solutions having increased ozone content
US5624535A (en) * 1994-10-20 1997-04-29 Hoshizaki Denki Kabushiki Kaisha Production system of electrolyzed water
US5853562A (en) * 1994-06-30 1998-12-29 Toto Ltd. Method and apparatus for electrolyzing water
US6056666A (en) * 1998-07-28 2000-05-02 New Venture Gear, Inc. Synchronized range shift mechanism for transfer case
US6106691A (en) * 1998-02-12 2000-08-22 T.R.P Co., Ltd. Medical instrument sterilizing and washing method and apparatus
US6117285A (en) * 1994-08-26 2000-09-12 Medical Discoveries, Inc. System for carrying out sterilization of equipment
US6146586A (en) * 1998-05-28 2000-11-14 The Research And Development Intstitute Dual current method and apparatus for sterilization of medical devices
US6309523B1 (en) * 1997-04-02 2001-10-30 Eltech Systems Corporation Electrode and electrolytic cell containing same
US20020139689A1 (en) * 2001-02-01 2002-10-03 Vadim Zolotarsky Electrode coating and method of use in a reverse polarity electrolytic cell
US6514401B2 (en) * 2001-05-02 2003-02-04 Taiwan Power Company Anti-biofouling system
US6524475B1 (en) * 1999-05-25 2003-02-25 Miox Corporation Portable water disinfection system
US6736966B2 (en) * 1999-05-25 2004-05-18 Miox Corporation Portable water disinfection system
US20040195090A1 (en) * 2001-06-25 2004-10-07 Rysuhin Omasa Vibratingly stirring apparatus, and device and method for processing using the stirring apparatus
US20040195104A1 (en) * 2003-04-04 2004-10-07 Shinichiro Minato Method and apparatus for controlling concentration of electrolytic solution
US20060137973A1 (en) * 2004-11-24 2006-06-29 Miox Corporation Device and method for instrument steralization
US20080237054A1 (en) * 2006-11-28 2008-10-02 Miox Corporation Low Maintenance On-Site Generator
US20100187122A1 (en) * 2007-04-05 2010-07-29 Vadim Zolotarsky Method and system of electrolytic treatment
US7897022B2 (en) * 2005-06-10 2011-03-01 Process Solutions, Inc. Electrolytic cell and system for treating water

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59170282A (ja) * 1983-03-18 1984-09-26 Permelec Electrode Ltd 希薄苛性アルカリ水溶液の電解方法及びその装置
FR2628757B1 (fr) * 1988-03-17 1992-01-17 Atochem Procede de regulation d'une cellule d'electrolyse, son application a la production du chlore et de la soude par electrolyse du chlorure de sodium en solution
AUPM498394A0 (en) * 1994-04-12 1994-05-05 Berrett Pty Ltd Electrolytic water treatment
JP2000042556A (ja) * 1998-05-28 2000-02-15 Shimadzu Corp 電解水製造装置
JP2000189971A (ja) * 1998-12-28 2000-07-11 Ekowaado:Kk 電解水生成装置における電極板面への気泡付着防止方法
US7048842B2 (en) * 2001-06-22 2006-05-23 The Procter & Gamble Company Electrolysis cell for generating chlorine dioxide
JP2003094060A (ja) * 2001-09-27 2003-04-02 Denso Corp 電解装置
JP2004113873A (ja) * 2002-09-24 2004-04-15 Sanyo Electric Co Ltd 水処理装置
JP2004298832A (ja) * 2003-04-01 2004-10-28 Asahi Glass Engineering Co Ltd 電解水生成装置、電解水を生成する方法、電解次亜水生成装置及び電解次亜水を生成する方法
JP2005058947A (ja) * 2003-08-18 2005-03-10 Daikin Ind Ltd 電気分解方法及び電気分解装置
JP2005138093A (ja) * 2003-11-05 2005-06-02 Hokuetsu:Kk 自動分取回分電解装置および電解殺菌水調製方法
JP2005319427A (ja) * 2004-05-11 2005-11-17 K & K:Kk アルカリ水生成装置
JP2005350716A (ja) * 2004-06-10 2005-12-22 Wakamiya Kogyo Kk 水槽の電解殺菌装置
JP2006015264A (ja) * 2004-07-02 2006-01-19 Daikin Ind Ltd 電気分解装置及び電気分解方法
US7393440B2 (en) * 2005-05-09 2008-07-01 National Research Council Of Canada Hydrogen generation system

Patent Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234110A (en) * 1959-02-06 1966-02-08 Amalgamated Curacao Patents Co Electrode and method of making same
US4087337A (en) * 1977-05-25 1978-05-02 Diamond Shamrock Corporation Rejuvenation of the efficiency of sea water electrolysis cells by periodic removal of anodic deposits
US4088550A (en) * 1977-05-25 1978-05-09 Diamond Shamrock Corporation Periodic removal of cathodic deposits by intermittent reversal of the polarity of the cathodes
USRE32077E (en) * 1977-06-30 1986-02-04 Oronzio Denora Impianti Elettrochimici S.P.A. Electrolytic cell with membrane and method of operation
US4479864A (en) * 1982-08-04 1984-10-30 The Japan Carlit Co., Ltd. Anode for electrolysis of seawater
US4710233A (en) * 1984-08-20 1987-12-01 Siemens Aktiengesellschaft Method and apparatus for cleaning, disinfecting and sterilizing medical instruments
US4761208A (en) * 1986-09-29 1988-08-02 Los Alamos Technical Associates, Inc. Electrolytic method and cell for sterilizing water
US4767511A (en) * 1987-03-18 1988-08-30 Aragon Pedro J Chlorination and pH control system
FR2644155A1 (fr) * 1989-03-07 1990-09-14 Levart Michel Appareil de sterilisation electrolytique des eaux
US5316740A (en) * 1992-03-26 1994-05-31 Los Alamos Technical Associates, Inc. Electrolytic cell for generating sterilization solutions having increased ozone content
US5385711A (en) * 1992-03-26 1995-01-31 Los Alamos Technical Associates, Inc. Electrolytic cell for generating sterilization solutions having increased ozone content
US5254226A (en) * 1992-05-05 1993-10-19 Ad Rem Manufacturing, Inc. Electrolytic cell assembly and process for production of bromine
US5853562A (en) * 1994-06-30 1998-12-29 Toto Ltd. Method and apparatus for electrolyzing water
US6117285A (en) * 1994-08-26 2000-09-12 Medical Discoveries, Inc. System for carrying out sterilization of equipment
US5624535A (en) * 1994-10-20 1997-04-29 Hoshizaki Denki Kabushiki Kaisha Production system of electrolyzed water
US6309523B1 (en) * 1997-04-02 2001-10-30 Eltech Systems Corporation Electrode and electrolytic cell containing same
US6106691A (en) * 1998-02-12 2000-08-22 T.R.P Co., Ltd. Medical instrument sterilizing and washing method and apparatus
US6146586A (en) * 1998-05-28 2000-11-14 The Research And Development Intstitute Dual current method and apparatus for sterilization of medical devices
US6056666A (en) * 1998-07-28 2000-05-02 New Venture Gear, Inc. Synchronized range shift mechanism for transfer case
US6524475B1 (en) * 1999-05-25 2003-02-25 Miox Corporation Portable water disinfection system
US6736966B2 (en) * 1999-05-25 2004-05-18 Miox Corporation Portable water disinfection system
US20020139689A1 (en) * 2001-02-01 2002-10-03 Vadim Zolotarsky Electrode coating and method of use in a reverse polarity electrolytic cell
US6514401B2 (en) * 2001-05-02 2003-02-04 Taiwan Power Company Anti-biofouling system
US20040195090A1 (en) * 2001-06-25 2004-10-07 Rysuhin Omasa Vibratingly stirring apparatus, and device and method for processing using the stirring apparatus
US20040195104A1 (en) * 2003-04-04 2004-10-07 Shinichiro Minato Method and apparatus for controlling concentration of electrolytic solution
US20060137973A1 (en) * 2004-11-24 2006-06-29 Miox Corporation Device and method for instrument steralization
US7897022B2 (en) * 2005-06-10 2011-03-01 Process Solutions, Inc. Electrolytic cell and system for treating water
US20080237054A1 (en) * 2006-11-28 2008-10-02 Miox Corporation Low Maintenance On-Site Generator
US20100187122A1 (en) * 2007-04-05 2010-07-29 Vadim Zolotarsky Method and system of electrolytic treatment

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FR 2644155 _Partial_Translation *

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080237054A1 (en) * 2006-11-28 2008-10-02 Miox Corporation Low Maintenance On-Site Generator
US7922890B2 (en) * 2006-11-28 2011-04-12 Miox Corporation Low maintenance on-site generator
US11421337B2 (en) 2006-11-28 2022-08-23 De Nora Holdings Us, Inc. Electrolytic on-site generator
US10400349B2 (en) 2006-11-28 2019-09-03 De Nora Holdings Us, Inc. Electrolytic on-site generator
US20130199928A1 (en) * 2010-05-14 2013-08-08 Rico Reinders Device for producing an electrochemically activated solution by means of an electrolysis process
KR101980383B1 (ko) * 2010-08-06 2019-05-20 존슨 맛쎄이 퍼블릭 리미티드 컴파니 전기분해식 온-사이트 발전기
KR20130108546A (ko) * 2010-08-06 2013-10-04 마이옥스코포레이션 전기분해식 온-사이트 발전기
WO2012019016A3 (fr) * 2010-08-06 2012-05-31 Miox Corporation Générateur électrolytique embarqué
EP3257819A1 (fr) * 2010-08-06 2017-12-20 Johnson Matthey Public Limited Company Générateur électrolytique sur site
WO2012142435A3 (fr) * 2011-04-15 2014-03-13 Advanced Diamond Technologies, Inc. Système et procédé électrochimiques destinés à une génération sur site d'oxydants sous une densité de courant élevée
WO2012142435A2 (fr) * 2011-04-15 2012-10-18 Advanced Diamond Technologies, Inc. Système et procédé électrochimiques destinés à une génération sur site d'oxydants sous une densité de courant élevée
WO2012156671A2 (fr) 2011-05-17 2012-11-22 A-Zone Technologies Limited Cellule électrochimique et son procédé de fonctionnement
US8882972B2 (en) 2011-07-19 2014-11-11 Ecolab Usa Inc Support of ion exchange membranes
US8562810B2 (en) 2011-07-26 2013-10-22 Ecolab Usa Inc. On site generation of alkalinity boost for ware washing applications
US9045835B2 (en) 2011-07-26 2015-06-02 Ecolab Usa Inc. On site generation of alkalinity boost for ware washing applications
US20130193001A1 (en) * 2012-01-26 2013-08-01 Tennant Company Apparatus and Method for Generating Thermally-Enhanced Treatment Liquids
EP2904689A4 (fr) * 2012-10-05 2016-02-10 Miox Corp Génération sur site sans transformateur
US10113241B2 (en) * 2014-02-04 2018-10-30 Jeffrey Allen Kaiser Control board for controlling channel sequencing of positive and negative DC voltage and current
US20150222116A1 (en) * 2014-02-04 2015-08-06 Jeffrey Allen Kaiser Control board for controlling channel sequencing of positive and negative dc voltage and current
WO2019014467A1 (fr) * 2017-07-12 2019-01-17 Axine Water Technologies Inc. Mode de fonctionnement d'un système de traitement des eaux usées
US11608281B2 (en) 2017-07-12 2023-03-21 Axine Water Technologies Inc. Method of operating a wastewater treatment system
US11027991B2 (en) 2017-10-05 2021-06-08 ElectroSea, LLC Electrolytic biocide generating system for use on-board a watercraft
US11718542B2 (en) 2017-10-05 2023-08-08 ElectroSea, LLC Electrolytic biocide generating system for use on-board a watercraft
US11345621B2 (en) 2019-02-11 2022-05-31 ElectroSea, LLC Self-treating electrolytic biocide generating system with recirculation
US11866351B2 (en) 2019-02-11 2024-01-09 ElectroSea, LLC Self-treating electrolytic biocide generating system with recirculation
US11498855B2 (en) 2019-04-09 2022-11-15 ElectroSea, LLC Electrolytic biocide-generating unit
ES2841509A1 (es) * 2019-12-16 2021-07-08 Santana Ramirez Alberto Andres Proceso para la limpieza de superficies catódicas en celdas voltaicas

Also Published As

Publication number Publication date
WO2009155044A3 (fr) 2010-04-22
WO2009155044A2 (fr) 2009-12-23
JP2011522123A (ja) 2011-07-28
EP2286003A4 (fr) 2011-05-25
EP2286003A2 (fr) 2011-02-23
MX2010012917A (es) 2011-03-03
CA2763550A1 (fr) 2009-12-23

Similar Documents

Publication Publication Date Title
US11421337B2 (en) Electrolytic on-site generator
US20090229992A1 (en) Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators
US7922890B2 (en) Low maintenance on-site generator
AU2017225104B2 (en) Device for manufacturing sodium hypochlorite or hypochlorous acid and water treatment system in general
CN111065481A (zh) 使用电解处理水性基质以产生可溶的锡金属
JP3122342U (ja) アルカリ水生成装置
WO2008032946A1 (fr) Appareil pour la production d'hypochlorite de sodium
JP2000218271A (ja) 電解装置
EP1314699B1 (fr) Procédé de nettoyage d' un appareil pour la production d'eau electrolysée
US20060060787A1 (en) Carbonate scale detector
JP4204955B2 (ja) 電解水生成方法および装置
WO2018100354A1 (fr) Ensemble de cellules électrochimiques et son procédé de fonctionnement
JP2004113873A (ja) 水処理装置
KR20140140971A (ko) 총 잔류 산화물질 농도 측정 모듈
WO2016174783A1 (fr) Générateur d'eau électrolysée
JP2001327968A (ja) 電解水生成装置
WO2018100361A1 (fr) Ensemble de cellules électrochimiques et son procédé de fonctionnement
JP2003285064A (ja) 冷却水系の水処理方法
GB2556948A (en) Toilet assembly and method for its operation
JP2016209864A (ja) 電解水生成器
JPH10468A (ja) 電解水生成装置
JPH1076271A (ja) 次亜塩素酸殺菌水生成装置のｐＨ及び次亜塩素酸濃度維持運転方法及びこの方法を実施する制御手段を備えた次亜塩素酸殺菌水生成装置
KR20170024278A (ko) 해양구조물용 실버이온타입 청수 살균시스템
JPH1190440A (ja) 電解水生成器
JP2009195807A (ja) 電解水生成装置

Legal Events

Date Code Title Description
AS Assignment

Owner name: MIOX CORPORATION, NEW MEXICO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SANCHEZ, JUSTIN;SCHWARZ, KEVIN;HERRINGTON, RODNEY E.;REEL/FRAME:023002/0819;SIGNING DATES FROM 20090706 TO 20090707

STCB Information on status: application discontinuation

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

AS Assignment

Owner name: UNION BAY CAPTIAL PARTNERS I, LLC, WASHINGTON

Free format text: SECURITY INTEREST;ASSIGNOR:MIOX CORPORATION;REEL/FRAME:034609/0287

Effective date: 20141230

AS Assignment

Owner name: MIOX CORPORATION, NEW MEXICO

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:UNION BAY CAPTIAL PARTNERS I, LLC;REEL/FRAME:038176/0968

Effective date: 20160331