US20150068913A1 - Method and apparatus for controlling electrolytic processes - Google Patents

Method and apparatus for controlling electrolytic processes Download PDF

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Publication number
US20150068913A1
US20150068913A1 US14/020,062 US201314020062A US2015068913A1 US 20150068913 A1 US20150068913 A1 US 20150068913A1 US 201314020062 A US201314020062 A US 201314020062A US 2015068913 A1 US2015068913 A1 US 2015068913A1
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electrolysis
conductivity
value
circuitry
orp
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Skyler Guest
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/02Process control or regulation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/14Alkali metal compounds
    • C25B1/16Hydroxides
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/24Halogens or compounds thereof
    • C25B1/26Chlorine; Compounds thereof

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  • the electrolysis process In order to obtain the proper concentration of these solutions, the electrolysis process must ordinarily be monitored by continually checking the pH and/or oxidation reduction potential (ORP), of the solutions, and the process must be stopped either manually in response to the pH and/or ORP reaching a target value, or else automatically by control systems that can properly interpret such readings and halt the process.
  • ORP oxidation reduction potential
  • this critical deflection point occurs at approximately the optimal concentration of the solutions for sanitizing and degreasing purposes. This means that, for producing such solutions, the controlling conductivity sensors need not even be calibrated to specific values, or even capable of measuring specific values, but can control the processes simply by being able to identify this significant change in the rate of change of conductivity.
  • FIG. 1 is a graph depicting the results of the curves of the change of pH ( 1 ), conductivity ( 2 ) and ORP, ( 3 ) over time in the anolyte chamber of a process electrolyzing a brine solution to produce a Hypochlorous Acid solution.
  • FIG. 2 is a graph depicting curves of the change of pH ( 11 ), conductivity ( 12 ) and ORP ( 13 ) over time in the catholyte chamber of a process electrolyzing a brine solution to produce a Sodium Hydroxide solution.
  • This invention is an improvement upon the methods and apparatuses for electrolyzing a brine solution and passing it through appropriate ion transfer membranes, so as to produce Hypochlorous Acid (HCIO) and/or Sodium Hydroxide (NaOH) solutions, as known in the current art and as described, by way of example, in U.S. patent application Ser. No. 13/008,152, by John Kuiphoff; the disclosure of that application is incorporated herein by reference.
  • HCIO Hypochlorous Acid
  • NaOH Sodium Hydroxide
  • Measuring pH or ORP provides an accurate reading of the progress of the reaction; unfortunately, sensors that provide such readings are expensive, and susceptible to damage and going out of calibration, shortening their service intervals and further adding expense. It is possible to utilize pH or ORP sensors initially with a given apparatus in order to establish timing baselines, and subsequently simply control the process with a timer; unfortunately, fluctuations in water and salt purity and power supplies can affect the process in ways for which a timer cannot compensate, and over time the process will also inevitably be affected by deterioration of the efficacy of membranes and electrodes, again uncompensated for by a timer.
  • FIGS. 1 and 2 show analogous and equally pronounced and readily-indentifiable conductivity curves, while reference will generally be made to the curves and figures of FIG. 1 , it is understood that the disclosure applies similarly to the complementary process charted in FIG. 2 .
  • the slope of the anolyte conductivity curve 2 (in FIG. 1 ) can be seen to reach a critical deflection point at a conductivity reading of approximately 700 ⁇ S where it intersects with the pH curve 1 at a pH reading of approximately 4.5, with an ORP of approximately 190 mV, after an elapsed reaction time of around 2250 seconds. It can also be seen that while the slope of the pH curve 1 is generally linear, there is a short, more acute slope to that curve centered on this intersection. This “kink” in the conductivity curve just happens to occur at, or very near, the optimum concentration of HCIO for use as sanitizer. Because of the distinct change in the slope of the conductivity curve at this critical point, it is alternatively possible to control this anolyte process with a sensor that simply measures when the rate of change in conductivity increases markedly, rather than specifying a particular conductivity value.
  • the slope of the catholyte conductivity curve 12 does not display a similar kink when the pH reaches the optimum concentration of NaOH for use as a degreaser, which is again at around the 2250 seconds mark, at a conductivity reading of approximately 1250 ⁇ S, a pH of around 10.8 and an ORP reading near ⁇ 130 mV.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

A method and apparatus for economically, reliably and efficiently controlling electrolytic processes by measuring the conductivity of the product of the electrolysis, and having the process terminate when a specified conductivity value is reached, that value corresponding to a desired pH and/or ORP value.

Description

    BACKGROUND OF THE INVENTION
  • Electrolyzing a brine solution and passing it through an appropriate ion transfer membrane, so as to produce Hypochlorous Acid (HCIO) and/or Sodium Hydroxide (NaOH) solutions, has been know for decades. In the proper concentrations, these solutions are particularly effective and ecologically benign sanitizers and degreasers, respectively, and the efficient production of such solutions was the inspiration for the parent application of this application, noted above, the disclosure of which is included herein by reference. In order to obtain the proper concentration of these solutions, the electrolysis process must ordinarily be monitored by continually checking the pH and/or oxidation reduction potential (ORP), of the solutions, and the process must be stopped either manually in response to the pH and/or ORP reaching a target value, or else automatically by control systems that can properly interpret such readings and halt the process.
  • Existing pH and ORP sensors, unfortunately, are expensive, vulnerable and finicky devices, requiring frequent cleaning and recalibration. Given the perils inherent in relying on a mis-reading or malfunctioning pH or ORP sensor, it is easily understood that it is desirable to come up with a simple and reliable method for monitoring and controlling this process, which is what this invention provides.
  • BRIEF SUMMARY OF THE INVENTION
  • It has been discovered that, as such an electrolysis process progresses, a chart showing the electrical conductivity of the produced solution changes in a largely linear manner plotted against the elapsed time of the process, right up until a critical deflection point is reached; at that point, the slope of that curve becomes significantly more acute, proceeding again in a largely linear manner from that point. Conductivity sensors are much simpler and less maintenance-intensive than pH and ORP sensors, and so controlling such electrolysis processes with conductivity sensors rather than pH or ORP sensors offers greater reliability and security to permit highly automated processes with infrequent need for outside intervention and maintenance.
  • In addition, it happens that this critical deflection point occurs at approximately the optimal concentration of the solutions for sanitizing and degreasing purposes. This means that, for producing such solutions, the controlling conductivity sensors need not even be calibrated to specific values, or even capable of measuring specific values, but can control the processes simply by being able to identify this significant change in the rate of change of conductivity.
  • Thus, controlling such electrolytic processes with the aid of conductivity sensors provides significant advantages of cost, simplicity and reliability.
  • BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
  • FIG. 1 is a graph depicting the results of the curves of the change of pH (1), conductivity (2) and ORP, (3) over time in the anolyte chamber of a process electrolyzing a brine solution to produce a Hypochlorous Acid solution.
  • FIG. 2 is a graph depicting curves of the change of pH (11), conductivity (12) and ORP (13) over time in the catholyte chamber of a process electrolyzing a brine solution to produce a Sodium Hydroxide solution.
  • DETAILED DESCRIPTION OF THE INVENTION
  • This invention is an improvement upon the methods and apparatuses for electrolyzing a brine solution and passing it through appropriate ion transfer membranes, so as to produce Hypochlorous Acid (HCIO) and/or Sodium Hydroxide (NaOH) solutions, as known in the current art and as described, by way of example, in U.S. patent application Ser. No. 13/008,152, by John Kuiphoff; the disclosure of that application is incorporated herein by reference.
  • Some method for measuring the progress of such an electrolyzing process must be provided, so that the process can be arrested before the products become too acidic and/or too alkaline. In the current art, this is provided by measuring either the pH or the ORP of the product(s) or, more crudely, by simple timed control of the process; all three methods have their drawbacks.
  • Measuring pH or ORP provides an accurate reading of the progress of the reaction; unfortunately, sensors that provide such readings are expensive, and susceptible to damage and going out of calibration, shortening their service intervals and further adding expense. It is possible to utilize pH or ORP sensors initially with a given apparatus in order to establish timing baselines, and subsequently simply control the process with a timer; unfortunately, fluctuations in water and salt purity and power supplies can affect the process in ways for which a timer cannot compensate, and over time the process will also inevitably be affected by deterioration of the efficacy of membranes and electrodes, again uncompensated for by a timer.
  • It is clear that a means of controlling these processes that provides the precision of pH or ORP sensors while avoiding their drawbacks is needed, and that is precisely what is achieved by controlling such processes by measuring the conductivity of the products.
  • As FIGS. 1 and 2 show analogous and equally pronounced and readily-indentifiable conductivity curves, while reference will generally be made to the curves and figures of FIG. 1, it is understood that the disclosure applies similarly to the complementary process charted in FIG. 2.
  • The slope of the anolyte conductivity curve 2 (in FIG. 1) can be seen to reach a critical deflection point at a conductivity reading of approximately 700 μS where it intersects with the pH curve 1 at a pH reading of approximately 4.5, with an ORP of approximately 190 mV, after an elapsed reaction time of around 2250 seconds. It can also be seen that while the slope of the pH curve 1 is generally linear, there is a short, more acute slope to that curve centered on this intersection. This “kink” in the conductivity curve just happens to occur at, or very near, the optimum concentration of HCIO for use as sanitizer. Because of the distinct change in the slope of the conductivity curve at this critical point, it is alternatively possible to control this anolyte process with a sensor that simply measures when the rate of change in conductivity increases markedly, rather than specifying a particular conductivity value.
  • The slope of the catholyte conductivity curve 12 (in FIG. 2) does not display a similar kink when the pH reaches the optimum concentration of NaOH for use as a degreaser, which is again at around the 2250 seconds mark, at a conductivity reading of approximately 1250 μS, a pH of around 10.8 and an ORP reading near −130 mV.
  • Experimentation has shown that, barring contamination of the process with foreign matter that materially alters the conductivity of the solution, the conductivity reading for a particular process in a particular apparatus is consistently predictable for a particular pH and/or ORP reading; in other words, for the purposes of monitoring and controlling such electrolytic processes, measuring conductivity is as accurate and reliable as measuring pH or ORP, and significantly more easily and economically achieved.
  • While this invention is inspired by a need to improve brine electrolysis processes, it can readily be seen that it can be effectively applied to a wide variety of electrolytic processes, and should not be read as being limited to brine electrolysis.

Claims (8)

I claim:
1. An apparatus for the electrolysis of an electrolyte, further comprising one or more sensors which measure the conductivity of the product or products of the electrolysis.
2. The apparatus of claim 1, further comprising circuitry or mechanism which controls the electrolysis according to conductivity measurements obtained by the one or more sensors.
3. The apparatus of claim 2, wherein the circuitry or mechanism which controls the electrolysis terminates the electrolysis when a conductivity measurement reaches a predetermined value.
4. The apparatus of claim 3, wherein the predetermined value of the conductivity measurement is that value that correlates to a desired pH and/or oxidation reduction potential value.
5. The method of electrolyzing an electrolyte, comprising having circuitry or mechanism control the electrolysis according to measurements of the conductivity of the product or products of the electrolysis.
6. The method of claim 5, further comprising having the circuitry or mechanism which controls the electrolysis terminate the electrolysis when a conductivity measurement reaches a predetermined value.
7. The method of claim 6, wherein the predetermined value of the conductivity measurement is that value that correlates to a desired pH and/or oxidation reduction potential value.
8. The apparatus of claim 2, wherein the circuitry or mechanism which controls the electrolysis terminates the electrolysis when the rate of change over time of conductivity measurements of the anolyte product of the electrolysis changes significantly.
US14/020,062 2013-09-06 2013-09-06 Method and apparatus for controlling electrolytic processes Abandoned US20150068913A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020259888A1 (en) * 2019-06-24 2020-12-30 Siemens Aktiengesellschaft Electrolysis system and method for storing electric energy using the electrolysis system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445722A (en) * 1993-02-22 1995-08-29 Nippon Intek Co., Ltd. Method and device for producing electrolytic water
US5624535A (en) * 1994-10-20 1997-04-29 Hoshizaki Denki Kabushiki Kaisha Production system of electrolyzed water
US20120145537A1 (en) * 2010-12-09 2012-06-14 John Kuiphoff Compact closed-loop electrolyzing process and apparatus
US20130199928A1 (en) * 2010-05-14 2013-08-08 Rico Reinders Device for producing an electrochemically activated solution by means of an electrolysis process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445722A (en) * 1993-02-22 1995-08-29 Nippon Intek Co., Ltd. Method and device for producing electrolytic water
US5624535A (en) * 1994-10-20 1997-04-29 Hoshizaki Denki Kabushiki Kaisha Production system of electrolyzed water
US20130199928A1 (en) * 2010-05-14 2013-08-08 Rico Reinders Device for producing an electrochemically activated solution by means of an electrolysis process
US20120145537A1 (en) * 2010-12-09 2012-06-14 John Kuiphoff Compact closed-loop electrolyzing process and apparatus

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020259888A1 (en) * 2019-06-24 2020-12-30 Siemens Aktiengesellschaft Electrolysis system and method for storing electric energy using the electrolysis system
EP3757253A1 (en) * 2019-06-24 2020-12-30 Siemens Aktiengesellschaft Electrolysis system and method for storing electric energy using the electrolysis system

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