WO2018151187A1 - 測定装置 - Google Patents

測定装置 Download PDF

Info

Publication number
WO2018151187A1
WO2018151187A1 PCT/JP2018/005158 JP2018005158W WO2018151187A1 WO 2018151187 A1 WO2018151187 A1 WO 2018151187A1 JP 2018005158 W JP2018005158 W JP 2018005158W WO 2018151187 A1 WO2018151187 A1 WO 2018151187A1
Authority
WO
WIPO (PCT)
Prior art keywords
ultraviolet light
measured
water
electrode
light source
Prior art date
Application number
PCT/JP2018/005158
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
水川　洋一
Original Assignee
ウシオ電機株式会社
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
Application filed by ウシオ電機株式会社 filed Critical ウシオ電機株式会社
Priority to KR1020197023104A priority Critical patent/KR102242895B1/ko
Priority to CN201880009382.0A priority patent/CN110234987A/zh
Publication of WO2018151187A1 publication Critical patent/WO2018151187A1/ja

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/06—Investigating concentration of particle suspensions
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
    • 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
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • 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

Definitions

  • the present invention relates to a measuring device for measuring the concentration of a substance to be measured based on the amount of change in conductivity caused by irradiating the water to be measured with ultraviolet light, and more specifically to the measurement of the concentration of organic matter contained in ultrapure water
  • the present invention relates to a measuring device suitably used for
  • the organic substances are decomposed by the action of the ultraviolet rays to generate carbon dioxide, and the carbon dioxide is dissolved in water
  • carbonate ions are generated to change the conductivity of the water to be measured. That is, in the water to be measured, the conductive substance generation reaction occurs by the irradiation of ultraviolet rays to generate carbonate ions which are the conductive substance, whereby the conductivity is increased. Therefore, the TOC can be detected based on the value of the amount of change (measured value) by measuring the amount of change in the conductivity of the water to be measured due to ultraviolet irradiation using the conductivity measuring means.
  • a method for measuring the conductivity of the liquid for example, an alternating current two-electrode method, an electromagnetic induction method and the like can be mentioned.
  • Patent Document 1 as a device for performing a method of measuring TOC using a change in conductivity due to irradiation of ultraviolet light in the water to be measured, a conductive consisting of a low pressure mercury lamp (ultraviolet light source) and a pair of electrode bodies There is disclosed a total organic carbon measuring apparatus (TOC measuring apparatus) provided with a rate measuring electrode (conductivity measuring means).
  • TOC measuring apparatus total organic carbon measuring apparatus
  • This TOC measurement device is configured to measure the conductivity by an alternating current two-electrode method.
  • the TOC measurement device according to Patent Document 1 includes a cylindrical low-pressure mercury lamp, and a right circular tubular cell disposed in parallel along the lamp axis of the low-pressure mercury lamp opposite to the low-pressure mercury lamp.
  • An inlet pipe formed on one end side of the cell and an outlet pipe formed on the other end side of the cell, and the inside of the cell is mutually separated along the central axis (tube axis) of the cell And a pair of electrode bodies disposed opposite to each other.
  • the pair of electrode bodies is in the shape of a bar, and is disposed in the vicinity of the central axis of the cell, and is symmetrical with respect to the central axis of the cell.
  • the inventors of the present invention have intensively studied the measuring apparatus for measuring the concentration of the substance to be measured based on the amount of change in conductivity caused by irradiating the water to be measured with ultraviolet light.
  • the object of the present invention is to provide a measuring device capable of measuring the concentration of a substance to be measured with high reliability without requiring a long time.
  • the measuring apparatus comprises a measured water storage container having an ultraviolet light transmitting portion for storing the measured water, and ultraviolet light through the ultraviolet light transmitting portion to the measured water stored in the measured water storage container. And a conductivity measuring electrode comprising a pair of electrode bodies which are disposed to face each other in the measurement water storage container.
  • the peripheral surface of the inter-electrode body region formed between the pair of electrode bodies is an ultraviolet light transmitting region in the ultraviolet light transmitting portion of the water container for measurement Is provided in contact with or in proximity to the inner surface of
  • the ultraviolet light source preferably emits light including ultraviolet light having a wavelength of 172 nm or less.
  • the ultraviolet light source is preferably a xenon excimer lamp.
  • a separation distance between the electrode body area and the inner surface of the ultraviolet ray transmitting area is 1.5 mm or less. Moreover, in such a measuring apparatus of this invention, it is still more preferable that the said separation distance is 1.0 mm or less.
  • the light from the ultraviolet light source may be irradiated to the water in a state where the water to be measured flows through the inside of the water container for measurement, and the water to be measured may be The light from the ultraviolet light source may be irradiated to the water in a state in which the water to be measured is retained inside the storage container.
  • the ultraviolet light source is turned off before measurement of the conductivity by the conductivity measuring electrode is started.
  • the ultraviolet light source and the pair of electrodes are disposed along the flow direction of the water to be measured inside the water container.
  • the ultraviolet ray transmitting portion is made of quartz glass,
  • the thickness of the ultraviolet ray transmitting portion is preferably 0.1 to 1.0 mm.
  • a purge means for purging the space between the ultraviolet light source and the water-to-be-measured container with an inert gas.
  • the inter-electrode region formed between the pair of electrode members constituting the conductivity measuring electrode is located in the vicinity of the ultraviolet light transmitting region in the ultraviolet light transmitting portion of the water container for measurement. ing. Therefore, even if the light from the ultraviolet light source contains ultraviolet light in a wavelength range where the light is easily absorbed by water, the conductive substance generation reaction by the ultraviolet light occurs in the region between the electrodes, or the generated conductive material is immediately It will be diffused to the interbody region. As a result, the ultraviolet light source is turned on, and the measurement of the conductivity is stably performed by the conductivity measuring electrode within a short time after the start of the irradiation of the ultraviolet light to the water to be measured. Can be measured. Therefore, according to the measuring device of the present invention, the concentration of the substance to be measured can be measured with high reliability without requiring a long time.
  • the measuring apparatus of the present invention even if the water to be measured contains a hard-to-degrade substance as the object to be measured because the ultraviolet light source emits light including ultraviolet light having a wavelength of 172 nm or less.
  • the degradable substance can be decomposed by the action of ultraviolet light having a wavelength of 172 nm or less. Therefore, the concentration of the substance to be measured can be measured with higher reliability without requiring a long time.
  • FIG. 3 is an explanatory exploded view showing a state in which the measured water storage container of FIG. 2 is disassembled along line AA in FIG. 2;
  • FIG. 3 is a perspective view for illustrating the inside of the measurement water storage container of FIG. 2 in the Z direction;
  • FIG. 5 is an explanatory cross-sectional view showing a cross section taken along line BB of FIG. 2;
  • It is a perspective view for explanation showing other examples of composition of a measuring device of the present invention.
  • FIG. 8 is an explanatory exploded view showing a state in which the measured water storage container of FIG. 7 is disassembled along the line AA in FIG. 7;
  • FIG. 8 is an explanatory cross-sectional view showing a cross section taken along line BB of FIG. 7;
  • It is a perspective view for description which shows the to-be-measured water storage container which comprises the measuring device of FIG. 11 is an exploded view for illustrating a state in which the measured water storage container constituting the measurement device of FIG. 10 is disassembled along the line AA in FIG.
  • FIG. 12 is an explanatory cross-sectional view showing a cross section taken along line BB of FIG. 11;
  • FIG. 1 is an explanatory perspective view showing an example of the configuration of the measuring apparatus of the present invention.
  • FIG. 2 is a perspective view for illustrating a measured water storage container constituting the measurement apparatus of FIG. 1
  • FIG. 3 is an exploded view of the measured water storage container of FIG. 2 along line AA in FIG.
  • FIG. 4 is a perspective view for illustrating the inside of the measurement water storage container of FIG. 2 in the Z direction.
  • 5 is a cross-sectional view for explaining the cross section taken along the line BB of FIG.
  • the measuring apparatus 10 includes a measuring water container 11 and a pair of electrodes 15 a and 15 b arranged to face each other in the measuring water container 11 so as to be separated. And an ultraviolet light source 20 disposed opposite to the water container 11.
  • the measuring apparatus 10 uses water containing an organic substance as a substance to be measured as the water to be measured, and measures the concentration (total organic carbon (TOC)) of the organic substance contained in the water to be measured. That is, the measuring device 10 is a total organic carbon measuring device (TOC measuring device) for measuring the concentration (TOC) of the organic substance contained in the ultrapure water.
  • TOC measuring device a total organic carbon measuring device for measuring the concentration (TOC) of the organic substance contained in the ultrapure water.
  • X direction the longitudinal direction of the end face portions 12a and 12b in the measured water storage container 11
  • the longitudinal direction is referred to as "Y direction”
  • the lateral direction of the end surface portions 12a and 12b and the side surface portions 13c and 13d is referred to as "Z direction”.
  • the ultraviolet light source 20 and the to-be-measured water storage container 11 are mutually spaced apart, and are arrange
  • the measured water storage container 11 is a rectangular solid internal space for storing the measured water, which is surrounded by the end surface portions 12a and 12b and the side surface portions 13a, 13b, 13c, and 13d constituting the rectangular parallelepiped container main body It has a water storage space), and is configured such that carbon dioxide in the atmosphere (air) constituting the measurement environment atmosphere is not taken into the water to be measured.
  • the measured water storage container 11 is made of an ultraviolet light transmissive material such as quartz glass, and thus the entire measured water storage container 11 is used as the ultraviolet light transmitting portion.
  • the ultraviolet ray transmitting portion at least a part of the ultraviolet ray transmitting portion is directly irradiated with the light L (ultraviolet ray) from the ultraviolet light source 20, and the light L (ultraviolet ray) from the ultraviolet light source 20 in the ultraviolet ray transmitting portion
  • the ultraviolet ray transmitting region R is constituted by the portion irradiated with Further, in the measured water storage container 11, a measured water supply port 17a is formed on one side (end surface 12a side) in the longitudinal direction (Y direction) of the side surface portion 13a, and in the side surface portion 13a A measured water discharge port 17b is formed on the other side (end face 12b side) in the longitudinal direction.
  • the measured water supply port 17a and the measured water discharge port 17b are provided in parallel in the longitudinal direction (Y direction) of the side surface portion 13a at the central portion in the lateral direction (X direction) of the side surface portion 13a. .
  • the measured water supplied from the measured water supply port 17a is directed to the measured water discharge port 17b. It distributes in the longitudinal direction (Y direction) of the water storage container 11.
  • the ultraviolet light source 20 is disposed to face the side surface portion 13b via a space and to extend in the longitudinal direction (Y direction) of the side surface portion 13b.
  • the ultraviolet light source 20 is disposed along the flow direction of the water to be measured in the inside of the water receiving container 11 (water receiving space) while being separated from the water receiving container 11. .
  • an ultraviolet ray transmitting region R is formed at the central portion in the lateral direction (X direction) of the side surface portion 13b so as to extend in the longitudinal direction (Y direction) of the side surface portion 13b.
  • the flow direction of the water to be measured is indicated by an arrow (two-dot dashed line arrow).
  • the ultraviolet ray transmission region R is shown by oblique lines (solid line oblique lines).
  • the ultraviolet ray transmitting portion (ultraviolet ray transmitting region R) is preferably thin from the viewpoint of suppressing the attenuation of ultraviolet rays.
  • the thickness of the ultraviolet ray transmitting region R in the ultraviolet ray transmitting portion is determined in accordance with the material of the ultraviolet ray transmitting portion (ultraviolet ray transmitting region R). Specifically, when the ultraviolet ray transmitting portion (ultraviolet ray transmitting region R) is made of quartz glass, the thickness of the ultraviolet ray transmitting portion (ultraviolet ray transmitting region R) is preferably 0.1 to 1.0 mm. Further, as shown in FIG. 1 to FIG. 3 and FIG.
  • the measured water storage container 11 is a flat container, and the dimension in the incident direction of the light L from the ultraviolet light source 20 (dimension in the Z direction Is preferably small.
  • the measured water storage container 11 has a container body inner size (the inner size of the measured water storage container 11 excluding the measured water supply port 17a and the measured water discharge port 17b)
  • the container has a wall thickness of 10 mm, a Y-direction dimension of 30 mm and a Z-direction dimension of 5 mm, and a wall thickness of 1.0 mm (the thickness of the end surface portions 12a and 12b and the side surface portions 13a, 13b, 13c and 13d).
  • Each of the pair of electrode bodies 15a and 15b constituting the conductivity measuring electrode extends along the longitudinal direction of the water container 11 to be measured (specifically, the side surface portions 13a, 13b, 13c and 13d) It is arranged.
  • Each of the pair of electrode bodies 15a and 15b is constituted by an electrode body plate member 19 which is longer than the dimension in the longitudinal direction (Y direction) of the water container 11 to be measured.
  • the plate member 19 for an electrode body is made of metal such as platinum, for example, and one end side portion constituting the electrode body 15a, 15b is positioned inside the measured water container 11 (container main body), and the other end side is an end face It protrudes outward from the portion 12a.
  • the other end of the electrode plate member 19 constitutes an external lead.
  • the two rectangular openings 14 extending in the lateral direction (Z direction) of the end face 12a in the end face 12a of the measured water storage container 11 are the longitudinal direction of the end face 12a. It is formed in parallel to the (X direction), and on the inner surface of the end surface 12b, the width direction (Z direction) of the end surface 12b is opposed to each of the two rectangular openings 14
  • the dimensions of the rectangular opening 14 are 2 mm in the X direction and 5 mm in the Z direction.
  • the other end of the electrode plate member 19 is inserted into the recess 16, and one end side portion of the plate member 19 protrudes outward of the measured water container 11 through the rectangular opening 14.
  • the electrode plate member 19 is inserted through the central portion of the rectangular opening 14 in which the sealing material layer 18 is formed.
  • the sealant that constitutes the sealant layer 18 is preferably resistant to ultraviolet light, and is one that does not have or does not have elution of an organic substance that causes an increase in TOC.
  • the peripheral surface of the inter-electrode body region S formed between the pair of electrode bodies 15a and 15b contacts or approaches the inner surface of the ultraviolet ray transmitting region R in the ultraviolet ray transmitting portion.
  • the pair of electrode bodies 15a and 15b are juxtaposed in the surface direction (specifically, the X direction) of the inner surface of the side surface portion 13b via the ultraviolet light transmission region R, and contact or proximity to the inner surface Provided.
  • the ultraviolet ray transmitting region R side (side surface portion in the circumferential surface of the inter-electrode body region S, specifically, each of the pair of electrode bodies 15a and 15b)
  • a virtual plane (hereinafter also referred to as a “virtual plane between electrode bodies”) including a portion located on the 13 b side) is brought into contact with or in proximity to the inner surface of the ultraviolet ray transmitting region R.
  • the plate member 19 for electrode bodies which comprises a pair of electrode bodies 15a and 15b has the same shape dimension.
  • the electrode plate member 19 (electrodes 15a and 15b) has a rectangular flat plate shape, and has a width (dimension in the Z direction) slightly smaller than the distance between the side portion 13a and the side portion 13b.
  • the dimensions of the pair of electrode bodies 15a and 15b are a thickness (dimension in the X direction) of 1.0 mm, a length (dimension in the Y direction) of 30.0 mm, and a width (dimension in the Z direction) of 2.0 mm.
  • the pair of electrode bodies 15a and 15b are disposed perpendicular to the side surfaces 13a and 13b and in parallel to the side surfaces 13c and 13d at positions near the side surface 13b.
  • a virtual plane between the electrode bodies including the side surface of one of the electrode bodies 15a and 15b is parallel to the side surface portion 13b and close to the inner surface of the side surface portion 13b.
  • the peripheral surface of the inter-electrode body region S is in a state in which it is close to the inner surface of the ultraviolet light transmitting region R. It is provided so as to extend in parallel to each other along the flow direction of the water to be measured in the storage space).
  • the distance between the electrode bodies of the pair of electrode bodies 15a and 15b is 1.0 mm.
  • the ultraviolet ray transmitting region R is indicated by solid line oblique lines
  • the inter-electrode body area S is indicated by dashed dotted line oblique lines.
  • the distance between the inter-electrode body region S and the inner surface of the ultraviolet light transmission region R d is appropriately determined according to the wavelength of the ultraviolet light in the light L from the ultraviolet light source 20.
  • the separation distance d is preferably 1.5 mm or less, and more preferably 1.0 mm or less.
  • the separation distance d is preferably 2.0 mm or less, and more preferably 1.5 mm or less. In the example of this figure, the separation distance d is 1.5 mm.
  • the ultraviolet light source 20 preferably emits light including ultraviolet light having a wavelength of 172 nm or less. Since the ultraviolet light source 20 emits light including ultraviolet light having a wavelength of 172 nm or less, the ultraviolet light having a wavelength of 172 nm or less has high energy, and a degradable substance (specifically, for example, urea) Since it can be decomposed, the concentration of the substance to be measured (specifically, TOC) can be measured with higher reliability.
  • a degradable substance specifically, for example, urea
  • a preferable specific example of the ultraviolet light source 20 that emits light including ultraviolet light having a wavelength of 172 nm or less includes a xenon excimer lamp.
  • the xenon excimer lamp is an ultraviolet radiation lamp having a peak wavelength of 172 nm.
  • a straight cylindrical xenon excimer lamp is used as the ultraviolet light source 20.
  • the ultraviolet light source 20 various types can be used as long as they emit ultraviolet light.
  • a low pressure mercury lamp etc. that does not emit ultraviolet light having a wavelength of 172 nm or less can also be used.
  • the lighting conditions of the ultraviolet light source 20, specifically, the ultraviolet light intensity in the ultraviolet light transmitting region R may be at least the conductive material generation reaction in the water containing space to be measured. It is appropriately set in consideration of the material and thickness of the ultraviolet ray transmitting portion (ultraviolet ray transmitting region R) according to the type and the type of water to be measured. Further, the ultraviolet light intensity distribution in the ultraviolet light transmission region R may not be uniform.
  • the type of water the type of the substance to be measured (organic substance)
  • the type of the ultraviolet light source 20 the shape and dimensions of the water container 11 and the shape, material and arrangement position of the pair of electrode bodies 15a and 15b are set appropriately.
  • the ultraviolet light source 20 xenon excimer lamp
  • the ultraviolet light source 20 is turned on under the condition that the irradiance in the ultraviolet ray transmitting region R is 6.45 mW / cm 2 .
  • the space between the ultraviolet light source 20 and the water-to-be-measured container 11 is an inert gas such as nitrogen gas.
  • a purge means for purging is provided.
  • the purge means for example, an inert gas supply device for supplying an inert gas between the ultraviolet light source 20 and the measured water storage container 11 can be used. Since the space between the ultraviolet light source 20 and the measurement water container 11 is purged with the inert gas, the ultraviolet light (vacuum ultraviolet light) is absorbed by the ultraviolet absorbing gas (for example, oxygen) present in the atmosphere. It is possible to suppress the attenuation of the light L (ultraviolet light) from the ultraviolet light source 20 until it reaches the ultraviolet light transmission region R due to the above.
  • the ultraviolet absorbing gas for example, oxygen
  • the water to be measured at a predetermined temperature for example, 25 ° C.
  • a predetermined temperature for example, 25 ° C.
  • the light L (ultraviolet light) from the ultraviolet light source 20 is irradiated to the water to be measured through the ultraviolet light transmitting portion (ultraviolet light transmitting region R).
  • the ultraviolet light source 20 may be turned off after a predetermined time has elapsed since it was turned on.
  • the ultraviolet light source 20 irradiates ultraviolet light to the water to be treated contained in the water to be measured container 11 and then measures the conductivity using the conductivity measurement electrodes (a pair of electrode bodies 15a and 15b). It is preferable that the light be turned off before the start of the When the ultraviolet light source 20 is turned on during the measurement of the conductivity, the light L (ultraviolet light) from the ultraviolet light source 20 is emitted to the electrode bodies 15a and 15b in the measurement of the conductivity. It is necessary to consider the photoelectric effect.
  • the organic matter is decomposed by the action of the ultraviolet light to generate carbon dioxide, and the carbon dioxide is dissolved in the water. Since carbonate ions are generated, the conductivity of the water to be measured changes. That is, in the water to be measured, the conductive substance generation reaction occurs by the ultraviolet irradiation, and the conductivity is increased by the generation of carbonate ions which are the conductive substance. Then, the amount of change in conductivity in the water to be measured is measured by the electrodes for measuring conductivity (a pair of electrode bodies 15a and 15b), and the organic substance which is the object to be measured based on the measured value of the amount of change in conductivity.
  • the electrodes for measuring conductivity a pair of electrode bodies 15a and 15b
  • TOC Concentration
  • the peripheral surface of the inter-electrode body region S formed between the pair of electrode bodies 15a and 15b is in proximity to the inner surface of the ultraviolet light transmission region R in the water container 11 to be measured. It is assumed. Therefore, since the ultraviolet light in the light L from the ultraviolet light source 20 includes ultraviolet light in a wavelength range in which the light is easily absorbed by water (specifically, ultraviolet light having a wavelength of 190 nm or less), the conductive substance generation reaction by ultraviolet light is mainly measured Even in the case where the reaction occurs in the vicinity of the ultraviolet ray transmitting region R in the water storage container 11, the conductive substance generating reaction occurs in the interelectrode body area S, and carbonate ion (conductive substance) is generated. .
  • the measuring apparatus 10 when the light L (ultraviolet light) from the ultraviolet light source 20 is irradiated to the water to be measured in a state of flowing through the inside of the water container 11 (water receiving space)
  • the flow velocity of the water to be measured at a position near the ultraviolet ray transmitting region R where the reactive substance generation reaction occurs, that is, the position near the inner surface of the side portion 13b is smaller than the flow velocity at the center position of the water container 11
  • the decomposition of the organic matter by ultraviolet light is sufficiently performed. Therefore, even when the water to be measured flows in the inside of the water-to-be-measured container 11, the accurate TOC can be detected.
  • the same accurate TOC can be obtained. It can be detected.
  • the state in which the water to be measured is stagnated means that the water to be measured is filled in the inside (the water-containing space) of the water-to-be-measured container 11, but new from the water supply port 17a. Water to be measured is not supplied, and there is no flow velocity of the water to be measured inside the water-to-be-measured container 11.
  • the water to be measured contains a hard-to-degrade substance as a substance to be measured by using an ultraviolet light source 20 that emits light containing ultraviolet light having a wavelength of 172 nm or less.
  • the TOC can be measured with higher reliability without requiring a long time. The reason will be described in detail.
  • the ultraviolet light source 20 which emits high energy ultraviolet light of wavelength 172 nm or less such as an excimer lamp, ultraviolet light from a low pressure mercury lamp (specifically, ultraviolet light of wavelength 185 nm and ultraviolet light of wavelength 254 nm) Can decompose degradable substances that can not be decomposed.
  • the conductive substance producing reaction is closer to the ultraviolet light transmitting region R Will occur at
  • the circumferential surface of the inter-electrode body region S is in a state close to the inner surface of the ultraviolet ray transmitting region R in the water container 11 to be measured.
  • An active substance generation reaction occurs to generate carbonate ions (conductive substances). Therefore, TOC can be measured with higher reliability without requiring a long time.
  • the conductivity measuring electrode formed of a pair of circular rod-like electrode bodies as disclosed in Patent Document 1 is disposed in the vicinity of the central axis of a cell (a water storage container to be measured) having a right circular tubular shape.
  • a cell a water storage container to be measured
  • the concentration of the TOC is In order to make an accurate measurement, an extremely long measurement time is required as compared with the conventional TOC measurement device.
  • the measuring apparatus of the present invention includes a measured water storage container, an ultraviolet light source, and an electrode for measuring conductivity, and an inter-electrode area formed between a pair of electrode bodies constituting the electrode for measuring conductivity.
  • the peripheral surface of the liquid crystal may be provided in a state of being in contact with or in proximity to the inner surface of the ultraviolet light transmitting region, and the configuration of the water container for measurement, the configuration of the ultraviolet light source, and the configuration of the conductivity measuring electrode (a pair of electrode bodies) Etc. are not particularly limited. Specifically, for example, in the measuring apparatus according to FIGS.
  • the ultraviolet ray transmitting region R may be formed on the side surface portion 13a, and the whole of the ultraviolet ray transmitting portion (a container of the water container 11 to be measured) The whole of the main body) may be configured. Moreover, the whole of the container main body of the to-be-measured water storage container 11 does not need to be made into an ultraviolet-ray transmission part. Further, the pair of electrode bodies 15a and 15b may not be disposed so that the virtual plane between the electrode bodies is in parallel to the ultraviolet ray transmitting region R, and may not be disposed in parallel to each other. It may have different geometric dimensions.
  • the ultraviolet light source 20 may not be disposed to extend in the flow direction of the water to be measured in the inside (the water receiving space of the water receiving container 11) of the water receiving container 11. It may be disposed so as to extend in a direction orthogonal to the flow direction of the water to be measured inside.
  • temperature measurement means may be provided inside the measured water storage container. As described above, when the temperature measuring means is provided, the conductivity is measured according to the temperature of the water to be measured measured by the temperature measuring means (specifically, the conductivity based on the measured current value) Temperature compensation can be performed.
  • the ultraviolet light source 20 may be a straight rectangular column.
  • the measuring apparatus according to FIG. 6 has the same configuration as the measuring apparatus 10 according to FIGS. 1 to 5 except that the shape of the ultraviolet light source 20 is different.
  • the pair of electrode bodies 15a and 15b is in the shape of a bar, that is, the pair of electrode bodies 15a and 15b is in the shape of a bar for the electrode body It may be configured by the member 26.
  • the measurement apparatus according to FIGS. 7 to 9 differs in that the shape of the pair of electrode bodies 15a and 15b is different, that is, the electrode body rod member 26 is used in place of the electrode body plate member 19.
  • the configuration is the same as that of the measuring device 10 according to FIGS.
  • the inter-electrode body region S formed between the pair of electrode bodies 15a and 15b is a pair of electrode bodies even when the pair of electrode bodies 15a and 15b have a curved surface such as a circular rod shape.
  • the rectangular flat plate 15a and 15b see FIG. 5
  • it is constituted by the space formed between the parts facing each other.
  • the measured water storage container 11 is made of quartz glass and the inner size of the container body (the inner size of the measured water storage container 11 excluding the measured water supply port 17a and the measured water outlet 17b) Are 10 mm in the X direction, 30 mm in the Y direction, and 5 mm in the Z direction, and the container thickness (the thickness of the end surface portions 12a and 12b and the side surface portions 13a, 13b, 13c, and 13d) is 1.0 mm. is there.
  • the dimensions of the two rectangular openings 14 formed in the end face portion 12a of the measured water storage container 11 are 2 mm in the X direction and 5 mm in the Z direction.
  • the electrode rod members 26 constituting the pair of electrode members 15a and 15b are made of platinum and have the same shape and size as each other, and the center of the rectangular opening 14 in which the sealing material layer 18 is formed. The part is inserted.
  • the pair of electrode bodies 15a and 15b are arranged to extend in parallel along the longitudinal direction of the side surface portions 13a, 13b, 13c and 13d. Then, a state in which the virtual inter-electrode body plane including the portion positioned on the side closest to the ultraviolet light transmission region R (side surface portion 13b) in the circumferential surface of each of the pair of electrode bodies 15a and 15b approaches the inner surface of the ultraviolet light transmission region R It is assumed.
  • the peripheral surface of the inter-electrode body region S is in a state in which it is close to the inner surface of the ultraviolet light transmitting region R. It is provided so as to extend in parallel to each other along the flow direction of the water to be measured in the storage space).
  • the dimensions of the pair of electrode bodies 15a and 15b are 0.75 mm in diameter and 30 mm in Y-direction (length). In addition, the distance between the electrode bodies of the pair of electrode bodies 15a and 15b is 1 mm. Moreover, the separation distance d is 1.5 mm.
  • the ultraviolet light source is turned on under the condition that the irradiance in the ultraviolet light transmission region R is 6.45 mW / cm 2 . In FIG. 9, the ultraviolet ray transmitting region R is indicated by solid line oblique lines, and the inter-electrode body area S is indicated by dashed dotted line oblique lines.
  • the measured water storage container 11 may be a straight cylindrical shape.
  • the measuring apparatus according to FIGS. 10 to 13 has the same configuration as the measuring apparatus 10 according to FIGS. 1 to 5 except that the shape of the measured water container 11 (container main body) is different.
  • the parallel direction of the pair of electrode bodies 15 a and 15 b is “X direction”
  • the length direction of the side surface portion 33 in the measured water storage container 11 Is referred to as “Y direction”
  • Z direction a direction perpendicular to a virtual plane between the electrode bodies
  • the measured water container 11 has the same configuration as the measuring device 10 according to FIGS. 1 to 5 except that the shape of the container body is a right cylindrical shape. It is a thing.
  • the measured water storage container 11 has a cylindrical internal space (measured water storage space) surrounded by the end surface portions 32a and 32b and the side surface portion 33 that constitute a cylindrical container body, and the measured water storage container 11
  • the water supply port 17a and the measured water discharge port 17b are juxtaposed in the Y direction so that the measured water supply port 17a is located on the end face 32a side and the measured water outlet 17b is located on the end face 32b. ing.
  • the measured water storage container 11 and the ultraviolet light source 20 are such that the ultraviolet light source 20, the measured water supply port 17a, and the measured water discharge port 17b face in the Z direction via the measured water storage space. It is arranged. That is, the measured water supply port 17 a and the measured water outlet 17 b are in a state of facing the ultraviolet ray transmitting region R.
  • the pair of electrode bodies 15a and 15b are arranged in the X direction and Z direction in a state in which the virtual plane between the electrode bodies including the side surface of one of the electrode bodies 15a and 15b (downward in FIG. 13) They are arranged in parallel in the direction and extend along the side surface portion 33 of the measured water container 11.
  • the measured water storage container 11 is made of quartz glass and the inner size of the container body (the inner size of the measured water storage container 11 excluding the measured water supply port 17a and the measured water outlet 17b) 10 mm in diameter and 30 mm in length (dimension in the Y direction), and the container thickness (the thickness of the end surface portions 32a and 32b and the side surface portion 33) is 1.0 mm.
  • the dimensions of the two rectangular openings 14 formed in the end face portion 32a of the measured water storage container 11 are 2 mm in the X direction and 5 mm in the Z direction.
  • the electrode plate member 19 constituting the pair of electrode members 15a and 15b is made of platinum and has the same shape and size, and the central portion of the rectangular opening 14 in which the sealing material layer 18 is formed. Through.
  • the dimensions of the pair of electrode bodies 15a and 15b are 1 mm in thickness (dimension in the X direction), 30 mm in length (dimension in the Y direction), and 2 mm in width (dimension in the Z direction).
  • the distance between the electrode bodies of the pair of electrode bodies 15a and 15b is 1 mm.
  • the separation distance d is 1.5 mm.
  • the ultraviolet light source 20 is turned on under the condition that the irradiance in the ultraviolet light transmission region R is 6.45 mW / cm 2 .
  • the ultraviolet ray transmitting region R is shown by solid hatching
  • the inter-electrode body region S is shown by dashed dotted hatching.
  • the measuring apparatus of this invention is not limited to a utilization application to a total organic carbon measuring apparatus. That is, in the measuring apparatus of the present invention, the substance to be measured is not limited to the organic substance, and any substance may be used as long as it causes a conductive substance generation reaction by being irradiated with ultraviolet light.
  • Example 1 A measuring device (hereinafter also referred to as “measuring device (1)”) was manufactured according to the configuration of FIGS. 7 to 9.
  • the produced measuring device (1) has the following specifications.
  • the prepared sample water for measurement (water to be measured) is supplied to the inside (the water containing space of the water for measuring water) through the water supply port for water to be measured.
  • the inside (measurement water storage space) of the measurement water storage container was filled with the sample water for measurement.
  • the ultraviolet light source is turned on under the condition that the irradiance in the ultraviolet ray transmitting portion (ultraviolet ray transmitting region R) is 6.45 mW / cm 2, and the ultraviolet light source is used for measuring sample water inside the measured water storage container.
  • the ultraviolet light source is turned off, and a sine wave with an applied voltage of 0.5 Vrms and a frequency of 1.0 kHz is applied between a pair of electrode bodies constituting the conductivity measurement electrode, and a current flowing between the pair of electrode bodies The current value was measured over time. And based on the obtained current value, the conductivity of the measurement sample water was calculated. That is, the conductivity of the measurement sample water inside the measured water storage container was measured by the alternating current two-electrode method. In this measuring device (1), the time required from when the ultraviolet light source is turned off to when the conductivity can be stably measured, that is, until it becomes possible to measure a constant conductivity.
  • Comparative Example 1 A measuring apparatus having the same configuration as that of the measuring apparatus (1) except that in the measuring apparatus (1) according to the first embodiment, the separation distance between the inter-electrode body area and the inner surface of the ultraviolet light transmitting area is 2.0 mm. (Hereafter, it is also called “the measurement apparatus for comparison (1).") was produced.
  • the conductivity of the sample water having a TOC value of 0.5 ppm and a conductivity of 0.10 ⁇ S / cm is stably measured in the same manner as in Example 1. I checked the time it took to be able to As a result, in the comparative measurement device (1), as described above, it is necessary to be able to measure the conductivity more stably than the measurement device (1) according to the first embodiment. The time was 50 times longer.
  • Example 2 In the measuring apparatus (1) according to the first embodiment, a measuring apparatus having the same configuration as that of the measuring apparatus (1) except that a low pressure mercury lamp is used as an ultraviolet light source (hereinafter also referred to as "measuring apparatus (2)”) Say).
  • the conductivity of the sample water for measurement having a TOC value of 0.5 ppm and a conductivity of 0.10 ⁇ S / cm can be stably measured. I checked the time it took to be able to do it. As a result, in the measuring apparatus (2), the time required to be able to stably measure the conductivity was substantially equal to that of the measuring apparatus according to Example 3 described later.
  • Example 3 A measuring apparatus having the same configuration as that of the measuring apparatus (2) except that in the measuring apparatus (2) according to the second embodiment, the separation distance between the inter-electrode body area and the inner surface of the ultraviolet light transmitting area is 2.0 mm. (Hereafter, it is also called "a measuring device (3).") was produced.
  • the conductivity of the sample water having a TOC value of 0.5 ppm and a conductivity of 0.10 ⁇ S / cm can be stably measured. I checked the time it took to be able to do it.
  • the measuring apparatus (3) as described above, the time required to be able to stably measure the conductivity can be approximately equal to that of the measuring apparatus (2) according to the second embodiment. there were.
  • measuring apparatus 11 measured water storage container 12a, 12b end surface part 13a, 13b, 13c, 13d side part 14 rectangular-shaped opening part 15a, 15b electrode body 16 recessed part 17a measured water supply port 17b measured water discharge port 18 sealing material Layer 19 plate member for electrode body 20 ultraviolet light source 26 rod member for electrode body 32a, 32b end face portion 33 side surface portion L light R ultraviolet ray transmission region S region between electrode bodies

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
PCT/JP2018/005158 2017-02-15 2018-02-15 測定装置 WO2018151187A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020197023104A KR102242895B1 (ko) 2017-02-15 2018-02-15 측정 장치
CN201880009382.0A CN110234987A (zh) 2017-02-15 2018-02-15 测量装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017025819A JP6926508B2 (ja) 2017-02-15 2017-02-15 測定装置
JP2017-025819 2017-02-15

Publications (1)

Publication Number Publication Date
WO2018151187A1 true WO2018151187A1 (ja) 2018-08-23

Family

ID=63170252

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/005158 WO2018151187A1 (ja) 2017-02-15 2018-02-15 測定装置

Country Status (4)

Country Link
JP (1) JP6926508B2 (zh)
KR (1) KR102242895B1 (zh)
CN (1) CN110234987A (zh)
WO (1) WO2018151187A1 (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60159642A (ja) * 1984-01-10 1985-08-21 アナテル・インスツルメント・コーポレーシヨン 超純水中の有機炭素含量を測定するための方法及びこの方法の実施に直接使用する装置
JPH09510791A (ja) * 1994-12-14 1997-10-28 アナテル・コーポレイション 光化学反応を監視するための改良セル及び回路
JP2001153828A (ja) * 1999-11-26 2001-06-08 Dkk Toa Corp 有機炭素含量の測定方法及び測定装置
JP2001183357A (ja) * 1999-12-27 2001-07-06 T & C Technical:Kk 全有機炭素測定システム用の酸化装置組立体
JP2001239275A (ja) * 2000-03-01 2001-09-04 Toto Ltd 水処理装置
US20110197660A1 (en) * 2008-10-16 2011-08-18 Veolia Water Solutions & Technologies Support Water purification apparatus

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63233370A (ja) * 1987-03-20 1988-09-29 Horiba Ltd 水中の全有機炭素測定装置
JP2001113163A (ja) * 1999-10-20 2001-04-24 Hoya Schott Kk 紫外光照射装置及び方法
US6741084B2 (en) * 2000-10-26 2004-05-25 Millipore Corporation Device for measuring the oxidizable carbon of a liquid and a method for the use thereof
JP4462099B2 (ja) * 2005-04-19 2010-05-12 株式会社島津製作所 全有機体炭素測定装置
JP5280038B2 (ja) * 2007-11-06 2013-09-04 野村マイクロ・サイエンス株式会社 超純水製造装置
JP2010216977A (ja) * 2009-03-17 2010-09-30 Shimadzu Corp 全有機体炭素測定装置
JP2010260021A (ja) * 2009-05-11 2010-11-18 Harison Toshiba Lighting Corp 紫外線照射装置
JP5496629B2 (ja) * 2009-12-08 2014-05-21 オルガノ株式会社 純水中の有機物分解装置および有機物分解方法
EP2803996A1 (fr) * 2013-05-15 2014-11-19 Merck Patent GmbH Dispositif de mesure de conductivité d'un liquide pour déterminer de très bas niveaux de carbone organique total (TOC) dans de l'eau pure et ultra-pure
CN105372300A (zh) * 2015-11-27 2016-03-02 上海康雷分析仪器有限公司 一种超纯水用toc检测装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60159642A (ja) * 1984-01-10 1985-08-21 アナテル・インスツルメント・コーポレーシヨン 超純水中の有機炭素含量を測定するための方法及びこの方法の実施に直接使用する装置
JPH09510791A (ja) * 1994-12-14 1997-10-28 アナテル・コーポレイション 光化学反応を監視するための改良セル及び回路
JP2001153828A (ja) * 1999-11-26 2001-06-08 Dkk Toa Corp 有機炭素含量の測定方法及び測定装置
JP2001183357A (ja) * 1999-12-27 2001-07-06 T & C Technical:Kk 全有機炭素測定システム用の酸化装置組立体
JP2001239275A (ja) * 2000-03-01 2001-09-04 Toto Ltd 水処理装置
US20110197660A1 (en) * 2008-10-16 2011-08-18 Veolia Water Solutions & Technologies Support Water purification apparatus

Also Published As

Publication number Publication date
JP6926508B2 (ja) 2021-08-25
KR102242895B1 (ko) 2021-04-21
CN110234987A (zh) 2019-09-13
JP2018132401A (ja) 2018-08-23
KR20190105043A (ko) 2019-09-11

Similar Documents

Publication Publication Date Title
KR100189794B1 (ko) 피처리물의 산화방법
CN101636652B (zh) 总有机碳测定装置
WO2014171138A1 (ja) 液体処理装置及び液体処理方法
Raeiszadeh et al. Microplasma UV lamp as a new source for UV-induced water treatment: Protocols for characterization and kinetic study
AU2001288246B2 (en) Wide-range TOC instrument using plasma oxidation
BRPI0706289A2 (pt) métodos e aparelhos para tornar lìquidos mais reativos
WO2016009624A1 (ja) 真空紫外光光源装置、光照射装置、及び自己組織化単分子膜のパターニング方法
KR101762394B1 (ko) 광이온화 가스센서
Maehara et al. Influence of conductivity on the generation of a radio frequency plasma surrounded by bubbles in water
JP4561448B2 (ja) 誘電体バリア放電ランプ及び紫外線照射装置
WO2018151187A1 (ja) 測定装置
JP5083825B2 (ja) 液体中プラズマ放電装置
Takahashi et al. Influence of reactor geometry and electric parameters on wastewater treatment using discharge inside a bubble
JP2018166028A (ja) 放電ランプ、オゾン生成装置およびオゾン生成方法
US20180313763A1 (en) Optical Detection of Tracer Gases in a Gas Discharge Cell Having Unexposed Electrodes
KR20110070827A (ko) 가스 방전 램프
JP2005222905A (ja) エキシマランプ
Matsuura et al. Reactive Radical Study Using Polyvinyl Alcohol-Potassium Iodide Solution as a New Chemical Probe
Abdelradi et al. Characterization of Atmospheric-Pressure DC-Glow Discharge in Contact with Liquid with a Miniature Argon Flow
JP2017188264A (ja) 液体処理用エキシマランプ
Piskarev et al. Formation of active species in spark corona discharge at a liquid electrode
Shi et al. Effect of supplied gas on ROS transport through liquid targets by plasma jet irradiation
Miichi pH Dependence on Decomposition of Persistent Organic Compounds in Water Using a DC Corona Discharger
Aristova et al. Plasma radiation-induced electrical conductivity of water
Müller Characterisation of cold atmospheric plasma afterglow for decontamination

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18755024

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197023104

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18755024

Country of ref document: EP

Kind code of ref document: A1