KR101733576B1 - Electrochemical TRO sensor - Google Patents

Electrochemical TRO sensor Download PDF

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Publication number
KR101733576B1
KR101733576B1 KR1020160008816A KR20160008816A KR101733576B1 KR 101733576 B1 KR101733576 B1 KR 101733576B1 KR 1020160008816 A KR1020160008816 A KR 1020160008816A KR 20160008816 A KR20160008816 A KR 20160008816A KR 101733576 B1 KR101733576 B1 KR 101733576B1
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South Korea
Prior art keywords
cell
electrode cell
flow cell
measurement
electrode
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KR1020160008816A
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Korean (ko)
Inventor
박규원
김성태
이해돈
박용석
김대원
이광호
김유진
하정한
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(주) 테크로스
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
    • G01N27/07—Construction of measuring vessels; Electrodes therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B13/00—Conduits for emptying or ballasting; Self-bailing equipment; Scuppers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63J—AUXILIARIES ON VESSELS
    • B63J4/00—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for
    • B63J4/002—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for for treating ballast water
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Ocean & Marine Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Public Health (AREA)
  • Toxicology (AREA)
  • Molecular Biology (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The present invention relates to an electrochemical TRO sensor comprising: a flow cell which is installed in a ballast pipe including an inlet to which ballast water flows and an outlet from which ballast water is discharged; a measurement electrode cell which comes in contact with the ballast water flowing in the flow cell, and measures a current value; a correction electrode cell which comes in contact with the ballast water flowing in the flow cell, is operated in accordance with a preset period, and measures a current value; and a controller which compares the measurement value of the measurement electrode cell with the measurement value of the correction electrode cell, corrects the measurement value of the measurement electrode cell when the comparison value deviates from a preset error range and calculates a remaining chlorine concentration. One electrode cell is used for measurement and the other electrode is used for correction, thereby correcting a decrease in measurement sensitivity and measuring an accurate TRO.

Description

Electrochemical TRO sensor < RTI ID = 0.0 >

TECHNICAL FIELD The present invention relates to an electrochemical sensor for measuring the residual chlorine concentration (TRO) of ballast water, and more particularly, to an electrochemical TRO sensor capable of correcting a decrease in sensitivity of a sensor.

In general, cargo vessels transported on the sea are mostly single-headed except for vessels that are traveling round-trip for the exchange of similar cargoes. When the ballast water is sailing under full load, ballast water (ballast water) is introduced into the ship for sailing in a ballast condition in order to improve the balance, safety and steering performance of the ship.

At this time, the ballast water is filled in one port and transferred to another, where it is discharged into a new port. As such, the release of marine organisms and pathogens contained in ballast water from a remote location is not only detrimental to the new environment, but can also be dangerous to both humans and animals in new ports.

In order to kill marine organisms and pathogens contained in such ballast water, oxidants are generally injected into the ballast tanks. Then neutralization treatment is carried out in order to neutralize the concentration of this oxidizing agent in accordance with legislation and regulations.

Among various sensors for measuring the oxidant concentration, the electrochemical sensor utilizes the phenomenon of receiving electrons or losing electrons by an electrochemical reaction at the surface of an electrode. The electrochemical sensor adjusts a potential or an electric current between electrodes, And the amount can be adjusted easily and quickly.

This principle has recently been used in the ship ballast water treatment field because the electrochemical sensor is easy to measure, has an early stabilization and quick response time, and has high sensitivity and specificity to the target analyte.

In general, a three-electrode cell composed of a working electrode, a reference electrode, and a counter electrode is generally used as the electrochemical sensor. Since the electrodes constituting the sensor are made of metals such as gold, silver and copper, Occurs or fouling occurs, and the sensitivity of the sensor is lowered, so that the accuracy of measurement may be lowered.
- Prior Art Document 1: Japanese Patent Laid-Open Publication No. 2013-134207 (Aug.
- Prior Art Document 2: Practical use of Japanese public Shinanpyeong 6-39329 (October 10, 1994)

delete

It is an object of the present invention to provide an electrochemical TRO sensor capable of accurately measuring TRO by correcting sensitivity degradation of a sensor.

According to an aspect of the present invention, there is provided a flow cell comprising: a flow cell installed in a ballast pipe having an inlet through which ballast water flows and an outlet through which ballast water flows; A measuring electrode cell for measuring a current value in contact with the ballast water flowing through the flow cell; A calibration electrode cell in contact with the ballast water flowing through the flow cell and operating according to a predetermined period to measure a current value; And comparing the measurement values of the measurement electrode cell and the correction electrode cell, and when the comparison value is out of the preset error range, correcting the measurement value of the measurement electrode cell to calculate the residual chlorine concentration.

Preferably, the measuring electrode cell and the correcting electrode cell are provided inside the flow cell.

Alternatively, the flow cell may comprise a first flow cell and a second flow cell disposed independently of each other, wherein the measuring electrode cell is disposed within the first flow cell, And is installed inside the flow cell.

Preferably, the first flow cell and the second flow cell are installed in parallel with the ballast piping, and the piping connecting between the first flow cell and the second flow cell is provided with an on / off valve Is installed.

Here, the controller obtains a correction coefficient for making the value of the current flowing through the measuring electrode cell equal to the value of the current flowing through the electrode cell for correction, multiplies the value of the current flowing through the measuring current cell by the correction coefficient, Is converted into the residual chlorine concentration value.

Preferably, when the correction coefficient is equal to or larger than a predetermined value, the controller alerts the replacement time of the electrode cell for measurement.

The ballast pipe may further include a strainer disposed at an inlet side of the ballast pipe to filter out foreign matter.

The electrochemical TRO sensor according to the present invention is composed of two electrode cells, one electrode cell is used for measurement, and the other electrode cell is used for correction, so that the measurement sensitivity can be compensated for and accurate TRO measurement is possible Do.

1 is a block diagram schematically illustrating an example of an electrochemical TRO sensor according to the present invention;
Figure 2 is a block diagram schematically illustrating a preferred example of an electrochemical TRO sensor according to the present invention;
3 is a flow chart schematically illustrating a method of calibrating a measured value of an electrochemical TRO sensor according to the present invention.

Hereinafter, preferred embodiments of the electrochemical TRO sensor according to the present invention will be described with reference to the accompanying drawings. In the following description of the present invention, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the technical scope of the present invention. Will be.

1, an electrochemical TRO sensor according to the present invention includes a flow cell 100 installed in a ballast pipe 10 through which ballast water flows, an electrode cell 200 for measuring a current value of the flow cell 100, A correction electrode cell 300 for providing a correction value for the measurement electrode cell 200 for measuring a current value separately from the measurement electrode cell 200 and a correction electrode 300 for correction based on the correction value of the correction electrode cell 300, And a controller (400) for correcting the measured value of the cell (200).

The flow cell 100 is installed in a ballast piping 10 through which ballast water flows. The ballast pipe (10) has an inlet (11) through which ballast water is introduced on the upstream side and an outlet (12) through which the ballast water is discharged on the downstream side. And the flow cell 100 is installed between the inlet 11 and the outlet 12 of the ballast piping 10 and configured to allow the ballast water to pass through.

The measuring electrode cell 200 contacts the ballast water flowing through the flow cell 100 to measure the current value. Here, the measuring electrode cell 200 is a three-electrode cell composed of a working electrode, a counter electrode, and a reference electrode. The measuring electrode cell 200 contacts the ballast water of the flow cell 100 to generate a current And the residual chlorine concentration (TRO) of the ballast water is measured.

The calibration electrode cell 300 is composed of three electrode cells in the same manner as the electrode cell for measurement 200, and contacts the ballast water of the flow cell 100 to measure the current value. Here, the correction electrode cell 300 operates in accordance with a predetermined cycle.

The controller 400 compares differences in residual chlorine concentration according to the measured values of the electrode cell for measurement 200 and the electrode cell for correction 300, for example, the current value or the current value, The residual chlorine concentration of the ballast water is calculated by correcting the measured value of the electrode cell 200 for measurement.

1, the flow cell 100 is composed of one cell, and the measuring electrode cell 200 and the correcting electrode cell 300 can be installed together in one flow cell 100. As shown in FIG. However, alternatively, as shown in FIG. 2, the flow cells may consist of a first flow cell 100A and a second flow cell 100B, which are arranged independently of each other. The measuring electrode cell 200 is installed inside the first flow cell 100A and the correction electrode cell 300 is installed inside the second flow cell 100B.

At this time, the first flow cell 100A and the second flow cell 100B are installed in parallel to the ballast pipe 10. Specifically, the first flow cell 100A is installed in the main flow path of the ballast piping 10, and the second flow cell 200B is installed in the path bypassed from the main flow path of the ballast piping 100. An on / off valve 500 is installed in the piping connecting the first flow cell 100A and the second flow cell 100B, that is, the bypass path. This on / off valve 500 is controlled by the controller 400 to allow ballast water to selectively flow into the second flow cell 100B.

Here, the controller 400 may apply a voltage to the correcting electrode cell 300 so that the correcting electrode cell 300 is operated according to the operation time or the number of times of the electrode cell 200 for measurement. When the calibration electrode cell 300 is operated, the on / off valve 500 may be opened to allow the ballast water to flow into the second flow cell 100B.

Further, the controller 400 obtains a correction coefficient for making the current value flowing in the measurement-use electrode cell 200 equal to the current value flowing in the correction-purpose electrode cell 300. Then, the controller 400 multiplies this correction coefficient by the current value flowing in the measurement current cell 200, and then converts the current value into the residual chlorine concentration value.

Preferably, the controller 400 determines that it is necessary to replace the measuring electrode cell 200 when the obtained correction coefficient is equal to or larger than the preset value, and notifies the replacement time of the measuring electrode cell 200 through the alarm have. For example, the controller 400 can display the replacement timing of the electrode cell 200 for measurement.

A strainer 600 may be provided on the upstream side of the ballast piping 10 to prevent foreign matter from flowing into the flow cell 100. A strainer 600 may be provided on the downstream side of the strainer 600, A pump 700 for supplying ballast water to the ballast water supply side is installed.

2 and 3, a method of calibrating a measured value of an electrochemical TRO sensor according to the present invention will be described.

First, a voltage is applied to the measuring electrode cell 200 to operate the measuring electrode cell 200 (S100). Then, the measurement electrode cell 200 measures the current value of the ballast water by the number of times set by a predetermined time interval under the control of the controller 400, and transmits the measured values to the controller 400.

Next, the controller 400 determines whether the electrode cell 200 for measurement has operated for the set number of times (S200). Specifically, the controller 400 checks the number of measured values transmitted from the measuring electrode cell 200, and determines whether the current value of the ballast water has been measured by the measuring electrode cell 200 a predetermined number of times. For example, the controller 400 can confirm the number of measured values transmitted from the measuring electrode cell 200.

If it is determined that the current value of the ballast water has been measured for the predetermined number of times, the controller 400 activates the correction electrode cell 300 (S300). The controller 400 opens the on / off valve 500 so that the ballast water flows into the second flow cell 100B side and the voltage is applied to the correction electrode cell 300 And transmits the measured current value to the controller 400.

Then, the controller 400 compares the measured value from the measuring electrode cell 200 with the measured value from the correcting electrode cell 300 (S400). Here, the controller 400 determines whether the difference between the measurement values of the measurement electrode cell 200 and the correction electrode cell 300 is out of the set error range.

As a result of comparison between the measured values, the controller 400 corrects the measured value of the electrode cell 200 for measurement (S500). Specifically, the controller 400 obtains a correction coefficient that makes the current value flowing through the measurement-purpose electrode cell 200 equal to the current value flowing through the correction-purpose electrode cell 300. Then, the controller 400 multiplies this correction coefficient by the current value flowing in the measurement current cell 200, and then converts the current value into the residual chlorine concentration value, thereby correcting the measured value of the electrode cell for measurement 200 .

When the difference between the measured values of the measurement electrode cell 200 and the correction electrode cell 300 is within the set error range, the controller 400 determines that the measured value of the electrode cell 200 for measurement Is directly converted into the residual chlorine concentration.

As described above, the electrochemical TRO sensor according to the present invention is composed of two electrode cells, one electrode cell is used for measurement, and the other electrode cell is used for correction, so that the decrease in measurement sensitivity can be corrected, Measurement is possible.

The embodiments of the present invention described above are merely illustrative of the technical idea of the present invention, and the scope of protection of the present invention should be interpreted according to the claims. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. It should be interpreted that it is included in the scope of right.

Claims (7)

A flow cell installed in a ballast pipe having an inlet through which ballast water flows and an outlet through which ballast water is discharged;
A measuring electrode cell for measuring a current value in contact with the ballast water flowing through the flow cell;
A calibration electrode cell in contact with the ballast water flowing through the flow cell and operating according to a predetermined period to measure a current value; And
And a controller for comparing measured values of the electrode cell for measurement and the electrode cell for correction and for calculating a residual chlorine concentration by correcting a measured value of the electrode cell for measurement when the comparison value is out of a predetermined error range,
Wherein the flow cell is comprised of a first flow cell and a second flow cell disposed independently of each other, the measurement electrode cell is disposed within the first flow cell, and the correction electrode cell is disposed within the second flow cell Installed,
Wherein the first flow cell is installed in the main flow path of the ballast piping and the second flow cell is installed in a path bypassed from the main flow path of the ballast piping and the connection between the first flow cell and the second flow cell Wherein an on / off valve controlled by the controller is installed in the piping.
The method according to claim 1,
Wherein the measuring electrode cell and the correcting electrode cell are installed inside the flow cell.
delete delete The method according to claim 1,
The controller obtains a correction coefficient for making the current value flowing through the measuring electrode cell equal to the current value flowing through the electrode cell for correction, multiplying the current value flowing through the measuring current cell by the correction coefficient, Concentration value of the TRO sensor.
6. The method of claim 5,
Wherein the controller alerts the replacing time of the measuring electrode cell when the correction coefficient is equal to or greater than a predetermined value.
The method according to claim 1,
Further comprising a strainer disposed at an inlet side of the ballast pipe to filter out foreign matter.
KR1020160008816A 2016-01-25 2016-01-25 Electrochemical TRO sensor KR101733576B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220085969A (en) * 2020-12-16 2022-06-23 주식회사 워터비 Residual chlorine meter having comparative measurement and self-calibration function

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220085969A (en) * 2020-12-16 2022-06-23 주식회사 워터비 Residual chlorine meter having comparative measurement and self-calibration function
KR102570508B1 (en) * 2020-12-16 2023-08-24 주식회사 워터비 Residual chlorine meter having comparative measurement and self-calibration function

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