Amperometric halogen control system

• US 6,238,555 B1
• Filed: 11/06/1998
• Issued: 05/29/2001
• Est. Priority Date: 11/07/1997
• Status: Expired due to Term

• Current Assignee: Balboa Water Group Incorporated
• Original Assignee: Bioquest, Co.
• Inventors: Calic, Caba, Milosavljevic, Emil, Silveri, Michael A.
• Primary Examiner(s): Simmons, David A.
• Assistant Examiner(s): LAWRENCE JR, FRANK M
• Application Number:
  US09/187,241
• Time in Patent Office: 935 Days
• Field of Search: 210/143, 210/192, 210/198.1, 210/243, 210/169, 210/96.1, 204/228.6
• US Class Current: 210/143
• CPC Class Codes: C02F 1/008 Control or steering systems not provided for elsewhere in subclass C02F
• CPC Class Codes: C02F 1/42 by ion-exchange ion-exchange in general B01J
• CPC Class Codes: C02F 1/46104 Devices therefor; Their operating or servicing
• CPC Class Codes: C02F 1/4674 with halogen or compound of halogens, e.g. chlorine, bromine
• CPC Class Codes: C02F 1/72 by oxidation C02F1/4672 takes precedence
• CPC Class Codes: C02F 1/766 by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
• CPC Class Codes: C02F 2001/46119 Cleaning the electrodes
• CPC Class Codes: C02F 2001/46123 Movable electrodes
• CPC Class Codes: C02F 2001/46128 Bipolar electrodes
• CPC Class Codes: C02F 2103/023 Water in cooling circuits
• CPC Class Codes: C02F 2103/42 from bathing facilities, e.g. swimming pools
• CPC Class Codes: C02F 2201/4611 Fluid flow
• CPC Class Codes: C02F 2201/4612 Controlling or monitoring
• CPC Class Codes: C02F 2201/46125 Electrical variables
• CPC Class Codes: C02F 2201/4617 DC only
• CPC Class Codes: C02F 2209/006 comprising a software program or a logic diagram
• CPC Class Codes: C02F 2209/06 pH
• CPC Class Codes: C02F 2303/04 Disinfection
• CPC Class Codes: G01N 27/4045 for gases other than oxygen
• CPC Class Codes: G01N 27/44 using electrolysis to generate a reagent, e.g. for titration
• CPC Class Codes: Y02W 10/37 : using solar energy

Abstract

An amperometric bromine control system accurately maintains a desired concentration of bromine within a home spa or in other water features. The control system employs amperometric sensing to measure the bromine concentration in the spa water and uses this measurement to control the electrochemical production of bromine through the oxidation of aqueous bromide. The level of bromide in the spa water desirably is greater than 50 ppm in order to obtain a linear relationship between the current level sensed through the amperometic measurement and the concentration level of bromine in the water. In this manner, the control system can accurately measure the bromine concentration in the spa water and precisely maintain the bromine concentration within a desired range between about 2 ppm and 6 ppm.

Claims

1. In combination, a water feature filled with water containing a sanitizing agent and an automatic sanitizing system comprising:

a sanitizing agent source communicating with the water in the water feature;

an amperometric sensor including a probe positioned in contact with water, wherein said probe includes a plurality of electrodes, said sensor generating an output signal indicative of the concentration of sanitizing agent in the water;

a control system receiving the signal from the sensor and operating the source at least between an active state and an inactive state depending on the concentration of the sanitizing agent in the water, whereby the concentration of the sanitizing agent in the water is automatically maintained within a preset range; and

wherein said control system also controls a cleaning cycle by causing different voltages to be applied sequentially between a plurality of said electrodes of said probe.

2. The combination of claim 1, wherein the sanitizing agent includes bromine.

3. The combination of claim 2, wherein the source comprises a sanitizing agent generator which includes at least one electrolytic cell.

4. The combination of claim 3, wherein the electrolytic cell has sufficiently sized electrodes to produce bromine at a rate of approximately 1-2 grams per hour.

5. The combination of claim 2, wherein the preset range for the bromine concentration is within the range of about 2 ppm to about 6 ppm.

6. The combination of claim 5, wherein the preset range for the bromine concentration is within the range of 2.5 ppm to 3.5 ppm.

7. The combination of claim 1, wherein the water contains an electrolyte prepared by the step of adding a salt composition comprising about 50 ppm sodium bromide and at least 500 ppm sodium chloride to the water.

8. The combination of claim 7, wherein the salt composition comprises no more than about 100 ppm of sodium bromide and no more than about 1200 ppm of sodium chloride.

9. The combination of claim 3, wherein the water feature additionally comprises a water line having influent and effluent ends through which the generator communicates with the water feature.

10. The combination of claim 9, wherein the probe of the sensor is arranged with the water line and is located downstream of the generator.

11. The combination of claim 9, wherein the generator includes at least one electrolytic cell and a pump which selectively circulates water through the water line.

12. The combination of claim 11, wherein the sensor comprises a potentiostat for amperometric measurements, the potentiostat being connected to the probe, and the control system including a microcontroller coupled to the potentiostat.

13. The combination of claim 12, wherein the microcontroller is coupled to the at least one electrolytic cell and to the pump of the generator for selectively operating both the electrolytic cell and the pump.

14. The combination of claim 1, wherein the water contains an electrolyte prepared by the step of adding a salt composition comprising at least about 50 ppm halide to the water.

15. The combination of claim 1, wherein the water contains an electrolyte prepared by the step of adding a salt composition comprising 300-1000 ppm bromide as sodium bromide to the water.

32. The system of claim 15, further comprising an electrical pump unit, wherein the microcontroller generates a first control signal to control the electrolytic cell and a second control signal to control the electrical pump unit.

16. An automatic sanitizing system comprising:

an electrolytic cell for emersion in water;

an amperometric sensor including;

a probe positionable in contact with the water, said probe comprising a plurality of electrodes, and

a potentiostat for amperometric measurements, the potentiostat being connected to the probe electrodes,

wherein the sensor generates an output signal indicative of a concentration of a chemical species in the water; and

a control system connected to the sensor to receive the output signal, and connected to the electrolytic cell to operate the electrolytic cell at least between active and inactive states depending on the concentration of the chemical species in the water, said control system comprising;

a microcontroller coupled to the potentiostat to selectively receive an output signal from the potentiostat which is indicative of the concentration of the sensed chemical species, and

a reference voltage unit that provides at least one reference voltage to the potentiostat,

wherein the microcontroller controls the reference voltage unit to apply the at least one reference voltage to the potentiostat, the reference voltage being preset within the control system and corresponding to the particular chemical species being sensed.

17. The system of claim 16, wherein the probe includes at least a working electrode, a reference electrode and a counter electrode.

18. The system of claim 17, wherein said microcontroller is connected to an indicator and controls the indicator to display whether the measured chemical species is within a preset range.

19. The system of claim 17, wherein the potentiostat includes a follower having an input connected to the reference electrode, and an inverting summing junction having an input coupled to an output of the reference voltage unit and to an output of the follower, and an output electrically coupled to the counter electrode.

20. The system of claim 17, wherein the potentiostat applies said reference voltage between said working electrode and said reference electrode.

21. The system of claim 17, wherein the control system further controls a cleansing cycle to cause a plurality of voltages to be applied in sequence between the working electrode and the counter electrode.

22. The system of claim 21, wherein at least one of the reference voltages is a negative potential and at least one of the reference voltages is a positive potential.

23. The system of claim 22, wherein a first reference voltage of said sequence of reference voltages has a value of +1 volts and is applied for one minute, a second reference voltage of said sequence of reference voltages has a value of −

80 millivolts and is applied for one minute, and a third voltage of said sequence of reference voltages has a value of +300 millivolts and is applied for one minute.

24. The system as claimed in claim 21, wherein the reference voltage unit generates a fourth reference voltage being selected to sense a chemical species other than the chemical species being sensed to control the electrolytic cell.

25. The system of claim 17, wherein the control system additionally includes a diagnostic system associated with the sensor probe for generating a signal indicative of a conductivity between the working electrode and the counter electrode, and the microcontroller receives said conductance signal and generates at least one control signal in response thereto.

26. The system of claim 25, wherein the diagnostic system includes a voltage divider with one element of the voltage divider comprising the variable impedance between the working electrode and the counter electrode.

27. The system of claim 26, wherein the diagnostic system comprises a diagnostic unit including a voltage sensor that is connected to the voltage divider and produces said conductivity signal.

28. The system of claim 26, wherein the microcontroller applies a signal with a frequency within the range between about 4 kHz and about 10 kHz to the voltage divider.

29. The system of claim 17, wherein the control system further comprises a temperature probe for measuring water temperature, said temperature probe generating a signal feedable to the microcontroller which generates at least one control signal in response at least in part thereto.

30. The system of claim 17, wherein the potentiostat and the probe of the amperometric sensor are remotely positioned relative to each other.

31. The system of claim 30, wherein a data transmission line connects the probe to the potentiostat, and the data transmission line is releasably connected to either the probe or the potentiostat.

33. The system of claim 17, wherein the potentiostat includes at least two operational amplifiers, each being provided with an asymmetrical power supply by an operational amplifier sub-power supply.

34. The system of claim 17, wherein the operational amplifier sub-power supply supplies each operational amplifier with about a positive potential of about +5 volts and a negative potential in the range of about −

4.2 volts and about −

4.5 volts.

35. An automatic sanitizing system comprising:

an electrolytic cell for emersion in water;

an amperometric sensor including a probe positionable in contact with the water, and wherein the sensor generates an output signal indicative of a concentration of a chemical species in the water;

a control system connected to the sensor to receive the output signal, and connected to the electrolytic cell to operate the electrolytic cell at least between active and inactive states depending on the concentration of the chemical species in the water;

a power supply unit providing power for the system; and

an isolator for electrically isolating the control system from at least the power supply unit and the electrolytic cell.

36. The system of claim 35, wherein the isolator includes an opto-coupler unit positioned between control signal outputs of the microcontroller and control signal inputs of the power supply unit, and between an input of the microcontroller and an output of the power supply unit.

37. The system of claim 36, wherein the isolator further includes a transformer having a first and second secondary winding, the first secondary winding providing power for the power supply unit and the electrolytic cell, and the second secondary winding providing power for the control system and the amperometric sensor.

38. In combination, a water feature filled with water containing an electrolyte prepared by the step of adding a salt composition comprising at least about 50 ppm halide to the water, and an automatic sanitizing system comprising:

a sanitizing agent source communicating with the water feature;

an amperometric sensor including a probe comprising a plurality of electrodes positioned in contact with the water, said sensor generating an output signal indicative of the concentration of the sanitizing agent in the water; and

a control system receiving the signal from the sensor and operating the sanitizing agent source at least between an active state, in which said source increases the concentration of the sanitizing agent in the water, and an inactive state depending on the concentration of the sanitizing agent in the water, whereby the concentration of the sanitizing agent in the water is automatically maintained within a preset range; and

wherein said control system also controls a cleaning cycle by causing different voltages to be applied sequentially between a plurality of said electrodes of said probe.

39. The combination of claim 38, wherein the sanitizing agent source includes a sanitizing agent generator.

40. The combination of claim 39, wherein the generator includes at least one electrolytic cell and a pump which selectively circulates water through the electrolytic cell.

41. The combination of claim 38, wherein the sanitizing agent source includes a dispenser containing the sanitizing agent.

42. The combination of claim 38, wherein the sanitizing agent includes bromine.

43. The combination of claim 38, wherein the water contains an electrolyte prepared by the step of adding a salt composition comprising 300-1000 ppm bromide as sodium bromide to the water.

44. An automatic sanitizing system comprising:

an electrolytic cell for emersion in water;

an amperometric sensor including a probe positionable in contact with the water, the sensor generating an output signal indicative of a concentration of a chemical species in the water;

a control system connected to the sensor to receive the output signal, and connected to the electrolytic cell to operate the electrolytic cell at least between active and inactive states depending on the concentration of the chemical species in the water;

a power supply unit for the electrolytic cell, the amperometric sensor and the control system; and

an isolator which electrically isolates the control system from the power supply unit and said electrolytic cell.

45. An automatic sanitizing system comprising:

a sanitizing agent source;

an amperometric sensor including a probe positionable in contact with water, the sensor generating an output signal indicative of a concentration of a sanitizing agent in the water, the probe includes at least a working electrode, a reference electrode and a counter electrode, and the sensor includes a potentiostat for amperometric measurements, the potentiostat being connected to the probe electrodes and including a follower having an input connected to the reference electrode, and an inverting summing junction having an input coupled to an output of the reference voltage unit and to an output of the follower, and an output electrically coupled to the counter electrode; and

a control system connected to the sensor to receive the output signal, and connected to the sanitizing agent source to operate the sanitizing agent source at least between active and inactive states depending on the concentration of the sanitizing agent in the water, wherein in the active state the sanitizing agent source is adapted to increase the concentration of the sanitizing agent in the water, the control system including a microcontroller coupled to the potentiostat to selectively receive the output signal from the potentiostat which is indicative of the concentration of the sensed chemical species, the control system further comprising a reference voltage unit that provides at least one reference voltage to the potentiostat.

46. The system of claim 45, wherein the sanitizing agent source includes a sanitizing agent generator.

47. The system of claim 45, wherein the microcontroller controls the reference voltage unit to apply the at least one reference voltage to the potentiostat, the voltage value being preset within the control system and corresponding to the particular chemical species being sensed.

48. The system of claim 47, wherein the potentiostat applies said reference voltage between said working electrode and said reference electrode.

49. The system of claim 48, wherein the control system further controls a cleansing cycle to cause different voltages to be applied in sequence between the working electrode and the counter electrode.

50. The system of claim 49, wherein at least one of the reference voltages is a negative potential and at least one of the reference voltages is a positive potential.

51. The system of claim 50, wherein a first reference voltage of said sequence of reference voltages has a value of +1 volts and is applied for one minute, a second reference voltage of said sequence of reference voltages has a value of −

0.08 volts and is applied for one minute, and a third voltage of said sequence of reference voltages has a value of +300 millivolts and is applied for one minute.

52. In combination, a water feature filled with water containing a sanitizing agent and an automatic sanitizing system comprising:

a sanitizing agent generator communicating with the water;

an amperometric sensor including a probe positioned in contact with water, said sensor generating an output signal indicative of the concentration of sanitizing agent in the water;

a control system receiving the signal from the sensor and operating the generator at least between an active state and an inactive state depending on the concentration of the sanitizing agent in the water, whereby the concentration of the sanitizing agent in the water is automatically maintained within a preset range;

a power supply unit for the sanitizing agent generator, the amperometric sensor, and the control system; and

an isolator which electrically isolates the control system from the power supply unit and the sanitizing agent generator.

53. The combination of claim 52, wherein the sanitizing agent includes bromine.

54. The combination of claim 53, wherein the sanitizing agent generator includes at least one electrolytic cell.

55. The combination of claim 54, wherein the electrolytic cell has sufficiently sized electrodes to produce bromine at a rate of approximately 1-2 grams per hour.

56. The combination of claim 53, wherein the preset range for the bromine concentration is within the range of about 2 ppm to about 6 ppm.

57. The combination of claim 56, wherein the preset range for the bromine concentration is within the range of 2.5 ppm to 3.5 ppm.

58. The combination of claim 52, wherein the water contains an electrolyte prepared by the step of adding a salt composition comprising about 50 ppm halide to the water.

59. The combination of claim 52, wherein the water contains an electrolyte prepared by the step of adding a salt composition comprising about 300-1000 ppm bromide as sodium bromide to the water.

60. The combination of claim 52, wherein the water feature additionally comprises a water line having influent and effluent ends that provide fluid communication with the water feature, said generator disposed relative to the water line such that fluid flow through said line is introduced into said generator.

61. The combination of claim 60, wherein the probe of the sensor is in the water line downstream of the generator.

62. The combination of claim 60, wherein the generator includes at least one electrolytic cell and a pump which selectively circulates water through the water line.

63. An automatic sanitizing system comprising:

an electrolytic cell for emersion in water;

an amperometric sensor including a probe positionable in contact with the water, the sensor generating an output signal indicative of a concentration of a chemical species in the water; and

a control system connected to the sensor to receive the output signal, and connected to the electrolytic cell to operate the electrolytic cell at least between active and inactive states depending on the concentration of the chemical species in the water;

wherein the probe includes at least a working electrode, a reference electrode and a counter electrode, and the sensor includes a potentiostat for amperometric measurements, the potentiostat being connected to the probe electrodes, and the control system including a microcontroller coupled to the potentiostat to selectively receive an output signal from the potentiostat which is indicative of the concentration of the sensed chemical species; and

wherein the control system additionally comprises a reference voltage unit that provides at least one reference voltage feedable to the potentiostat; and

wherein the potentiostat includes an inverter having an output connected to the counter electrode, a follower having an input connected to the reference electrode, and an inverting summing junction having an input coupled to an output of the reference voltage unit and to an output of the follower, and an output connected to an input of the inverter.

64. An automatic sanitizing system comprising:

an electrolytic cell for emersion in water;

an amperometric sensor including a probe positionable in contact with the water, the sensor generating an output signal indicative of a concentration of a chemical species in the water; and

a control system connected to the sensor to receive the output signal, and connected to the electrolytic cell to operate the electrolytic cell at least between active and inactive states depending on the concentration of the chemical species in the water;

wherein the probe includes at least a working electrode, a reference electrode and a counter electrode, and the sensor includes a potentiostat for amperometric measurements, the potentiostat being connected to the probe electrodes, and the control system including a microcontroller coupled to the potentiostat to selectively receive an output signal from the potentiostat which is indicative of the concentration of the sensed chemical species; and

wherein the control system additionally comprises a reference voltage unit that provides at least one reference voltage feedable to the potentiostat; and

wherein the microcontroller controls the reference voltage unit to apply the at least one reference voltage to the potentiostat, the voltage value being preset within the control system and corresponding to the particular chemical species being sensed.

65. The system of claim 64, wherein the potentiostat applies said reference voltage between said working electrode and said reference electrode.

66. The system of claim 64, wherein the control system further controls the reference voltage unit in a cleansing cycle to cause said reference voltage unit to output a sequence of three different reference voltages, said sequence of reference voltages applied to the potentiostat to produce said sequence of voltages between the working electrode and the counter electrode.

67. The system of claim 66, wherein at least one of the reference voltages is a negative potential and at least one of the reference voltages is a positive potential.

68. The system of claim 67, wherein a first reference voltage of said sequence of reference voltages has a value of +1 volts and is applied for one minute, a second reference voltage of said sequence of reference voltages has a value of −

80 millivolts and is applied for one minute, and a third voltage of said sequence of reference voltages has a value of +300 millivolts and is applied for one minute.

69. The system as claimed in claim 66, wherein the reference voltage unit generates a fourth reference voltage being selected to sense a chemical species other than the chemical species being sensed to control the electrolytic cell.

70. An automatic sanitizing system comprising:

an electrolytic cell for emersion in water;

an amperometric sensor including a probe positionable in contact with the water, the sensor generating an output signal indicative of a concentration of a chemical species in the water; and

a control system connected to the sensor to receive the output signal, and connected to the electrolytic cell to operate the electrolytic cell at least between active and inactive states depending on the concentration of the chemical species in the water;

wherein the probe includes at least a working electrode, a reference electrode and a counter electrode, and the sensor includes a potentiostat for amperometric measurements, the potentiostat being connected to the probe electrodes, and the control system including a microcontroller coupled to the potentiostat to selectively receive an output signal from the potentiostat which is indicative of the concentration of the sensed chemical species; and

wherein the control system additionally includes a diagnostic system associated with the sensor probe for generating a signal indicative of a conductivity between the working electrode and the reference electrode, and the microcontroller receives said conductance signal and generates at least one control signal in response thereto; and

wherein the diagnostic system includes a voltage divider with one element of the voltage divider comprising the variable impedance between the working electrode and the reference electrode.

71. The system of claim 70, wherein the diagnostic system comprises a diagnostic unit including a voltage sensor that is connected to the voltage divider and produces said conductivity signal.

72. The system of claim 70, wherein the microcontroller applies a signal with a frequency within the range between about 4 kHz and about 10 kHz to the voltage divider.

73. An automatic sanitizing system comprising:

an electrolytic cell for emersion in water;

an amperometric sensor including a probe positionable in contact with the water, the sensor generating an output signal indicative of a concentration of a chemical species in the water;

a control system connected to the sensor to receive the output signal, and connected to the electrolytic cell to operate the electrolytic cell at least between active and inactive states depending on the concentration of the chemical species in the water;

a power supply unit providing power for the system; and

an isolator for electrically isolating the control system from at least the power supply unit and the electrolytic cell;

wherein the probe includes at least a working electrode, a reference electrode and a counter electrode, and the sensor includes a potentiostat for amperometric measurements, the potentiostat being connected to the probe electrodes, and the control system including a microcontroller coupled to the potentiostat to selectively receive an output signal from the potentiostat which is indicative of the concentration of the sensed chemical species.

74. The system of claim 73, wherein the isolator includes an opto-coupler unit positioned between control signal outputs of the microcontroller and control signal inputs of the power supply unit, and between an input of the microcontroller and an output of the power supply unit.

75. The system of claim 74, wherein the isolator further includes a transformer having a first and second secondary winding, the first secondary winding providing power for the power supply unit and the electrolytic cell, and the second secondary winding providing power for the control system and the amperometric sensor.

76. An automatic sanitizing system comprising:

a sanitizing agent source;

an amperometric sensor including a probe positionable in contact with water, the sensor generating an output signal indicative of a concentration of a sanitizing agent in the water, the probe includes at least a working electrode, a reference electrode and a counter electrode, and the sensor includes a potentiostat for amperometric measurements, the potentiostat being connected to the probe electrodes and including at least two operational amplifiers, each being provided with an asymmetrical power supply by an operational amplifier sub-power supply; and

a control system connected to the sensor to receive the output signal, and connected to the sanitizing agent source to operate the sanitizing agent source at least between active and inactive states depending on the concentration of the sanitizing agent in the water, wherein in the active state the sanitizing agent source is adapted to increase the concentration of the sanitizing agent in the water, the control system including a microcontroller coupled to the potentiostat to selectively receive the output signal from the potentiostat which is indicative of the concentration of the sensed chemical species;

wherein the sanitizing agent source includes a sanitizing agent generator; and

wherein the control system additionally comprises a reference voltage unit that provides at least one reference voltage feedable to the potentiostat.

77. The system of claim 76, wherein the potentiostat includes an inverter having an output connected to the counter electrode, a follower having an input connected to the reference electrode, and an inverting summing junction having an input coupled to an output of the reference voltage unit and to an output of the follower, and an output connected to an input of the inverter.

78. The system of claim 76, wherein the microcontroller controls the reference voltage unit to apply the at least one reference voltage to the potentiostat, the voltage value being preset within the control system and corresponding to the particular chemical species being sensed.

79. The system of claim 78, wherein the potentiostat applies said reference voltage between said working electrode and said reference electrode.

80. The system of claim 79, wherein the control system further controls the reference voltage unit in a cleansing cycle to cause said reference voltage unit to output a sequence of three different reference voltages, said sequence of reference voltages applied to the potentiostat to produce said sequence of voltages between the working electrode and the counter electrode.

81. The system of claim 80, wherein at least one of the reference voltages is a negative potential and at least one of the reference voltages is a positive potential.

82. The system of claim 81, wherein a first reference voltage of said sequence of reference voltages has a value of +1 volts and is applied for one minute, a second reference voltage of said sequence of reference voltages has a value of −

0.08 volts and is applied for one minute, and a third voltage of said sequence of reference voltages has a value of +300 millivolts and is applied for one minute.