WO2021039392A1 - Dispositif de mesure de concentration d'acide peracétique - Google Patents

Dispositif de mesure de concentration d'acide peracétique Download PDF

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Publication number
WO2021039392A1
WO2021039392A1 PCT/JP2020/030656 JP2020030656W WO2021039392A1 WO 2021039392 A1 WO2021039392 A1 WO 2021039392A1 JP 2020030656 W JP2020030656 W JP 2020030656W WO 2021039392 A1 WO2021039392 A1 WO 2021039392A1
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WIPO (PCT)
Prior art keywords
peracetic acid
acid concentration
diaphragm
internal liquid
concentration meter
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PCT/JP2020/030656
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English (en)
Japanese (ja)
Inventor
佳彦 川口
智子 甲斐
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株式会社堀場アドバンスドテクノ
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Priority to JP2021542714A priority Critical patent/JP7489991B2/ja
Publication of WO2021039392A1 publication Critical patent/WO2021039392A1/fr

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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
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
    • 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
    • G01N27/416—Systems

Definitions

  • the present invention relates to a peracetic acid densitometer that measures the concentration of peracetic acid contained in a sample solution.
  • the peracetic acid concentration meter for example, there is a diaphragm type as described in Patent Document 1.
  • a diaphragm-type peracetic acid densitometer is provided with a diaphragm that selectively permeates peracetic acid, and the current change that occurs when the peracetic acid that has permeated the diaphragm undergoes a redox reaction on the surface of the working electrode. Is being measured.
  • the diaphragm that permeates peracetic acid also permeates hydrogen peroxide at the same time.
  • hydrogen peroxide permeates the diaphragm together with peracetic acid
  • hydrogen peroxide also reacts on the surface of the working electrode in the same manner as peracetic acid, so that there is a problem that an error occurs in the measurement of peracetic acid concentration.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a peracetic acid concentration meter capable of accurately measuring a peracetic acid concentration while suppressing an error due to hydrogen peroxide as small as possible. To do.
  • the peracetic acid concentration meter according to the present invention is a peracetic acid concentration meter of a diaphragm type for measuring the peracetic acid concentration of a sample solution, and the peracetic acid permeating the peracetic acid and the peracetic acid permeating the peracetic acid are dissolved. It is characterized by comprising an internal solution, an action electrode and a counter electrode immersed in the internal solution, and a catalyst for decomposing hydrogen peroxide in the internal solution.
  • the peracetic acid concentration meter configured in this way, since the catalyst for decomposing hydrogen peroxide in the internal liquid is provided, even if hydrogen peroxide permeates the diaphragm together with peracetic acid, it is contained in the internal liquid.
  • the concentration of hydrogen peroxide in the above can be suppressed sufficiently low. Therefore, the error caused by hydrogen peroxide contained in the internal liquid can be suppressed as small as possible, and the peracetic acid concentration can be measured more accurately than before.
  • the catalyst may be catalase.
  • the organic substance adheres to the surface of the diaphragm, or microorganisms propagate on the adhered organic substance to form a film, which adversely affects the measurement of peracetic acid concentration. May be given.
  • the cleaning of the diaphragm itself may be carried out because there is a risk of contamination of the sample solution by physical cleaning of a brush or the like or chemical contamination of the sample solution by chemical cleaning. It can be difficult.
  • a conductive mesh layer may be further provided on the surface of the diaphragm on the side in contact with the sample solution.
  • a predetermined voltage is applied to the conductive mesh layer, the organic matter adhering to the surface of the diaphragm can be decomposed and the growth of microorganisms can be suppressed.
  • the accuracy of peracetic acid concentration measurement can be further improved by decomposing and removing the peracetic acid remaining in the internal liquid.
  • a method of bringing the diaphragm into contact with zero water substantially free of peracetic acid for a predetermined time can be mentioned between the measurements.
  • the diaphragm while the diaphragm is in contact with zero water, peracetic acid does not enter the internal liquid, and the peracetic acid remaining in the internal liquid continues to be decomposed on the surface of the working electrode. .. Therefore, the peracetic acid concentration in the internal liquid can be reduced by providing a time for the diaphragm to be in contact with zero water. As a result, the measurement error due to the peracetic acid remaining in the internal liquid can be suppressed to a small value.
  • a light source for irradiating the peracetic acid concentration meter with ultraviolet rays In order to further improve the accuracy of the peracetic acid concentration measurement, it is preferable to provide a light source for irradiating the peracetic acid concentration meter with ultraviolet rays.
  • Ultraviolet rays decompose peroxides such as hydrogen peroxide to generate hydroxyl radicals. Hydroxyl radicals strongly decompose microorganisms and organic substances. Therefore, if a light source that irradiates the peracetic acid concentration meter with ultraviolet rays is provided, microorganisms and organic substances in the internal solution and the sample solution can be decomposed. As a result, for example, contamination of the working electrode surface and the diaphragm surface due to the adhesion of microorganisms and organic substances can be suppressed, and the measurement accuracy can be further improved.
  • the peracetic acid concentration measurement is provided with a peracetic acid concentration meter as described above and a flow path through which the sample solution flows, and the peracetic acid concentration of the sample solution flowing in the flow path is continuously measured using the peracetic acid concentration meter. It may be used as a device. In this case, a bypass flow path through which zero water flows may be provided separately from the main flow path through which the sample solution flows, and these may be switched at predetermined time intervals.
  • the error in the peracetic acid concentration measurement can be suppressed to a small value, and the peracetic acid concentration can be measured more accurately than before.
  • the schematic diagram of the peracetic acid concentration meter in one Embodiment of this invention. Schematic cross-sectional view of a peracetic acid densitometer according to an embodiment of the present invention. An enlarged cross-sectional view of an enlarged portion A of FIG. 3 in one embodiment of the present invention. An enlarged cross-sectional view of a portion A of FIG. 3 in another embodiment of the present invention.
  • the peracetic acid concentration meter in this embodiment is for immersing the peracetic acid concentration meter in a sample solution and measuring the peracetic acid concentration in the sample solution. Then, as shown in FIGS. 1 and 2, this peracetic acid concentration meter includes a container 1a for accommodating the internal liquid and a lid portion 1b for sealing the container 1a.
  • the container 1a has a hollow cylindrical shape with one end surface open and the other end surface closed, and when the lid portion 1b is attached so as to close the open end surface, the internal liquid 13 is accommodated therein. Space is formed. Further, a screw thread (not shown) for attaching the lid portion 1b is formed on the inner wall near the opening end.
  • a diaphragm 11 is provided on a part of the other end surface to allow a specific substance contained in the sample solution to permeate and penetrate into the container 1a.
  • the diaphragm 11 permeates peracetic acid, hydrogen peroxide, dissolved oxygen, residual chlorine, etc. in the sample solution, and is made of a material containing, for example, silicon, fluororesin, or polyethylene.
  • fluororesin for example, Teflon (registered trademark) or the like can be used.
  • film thickness of the diaphragm 11 for example, one having a thickness of 10 ⁇ m to 200 ⁇ m can be used.
  • the lid portion 1b seals the container 1a, and a holding member 16 for holding the working electrode 4 and the counter electrode 5 is provided so as to project from the substantially central portion on the container 1a side.
  • the holding member 16 is housed in a space formed between the container 1a and the lid 1b with the lid 1b attached to the container 1a. Further, on the opposite side of the container 1a side, a connector portion 6 to which a cable for connecting an external device is attached is provided.
  • the holding member 16 is made of an insulating material, and as shown in FIG. 3, surrounds the working pole 4 to hold the working pole 4, and winds and holds the counter electrode 5 around it. It is a thing. Further, the holding member 16 is provided with a spiral groove for attaching the lid portion 1b to the container 1a, and by fitting the lid portion 1b with a screw thread (not shown) provided on the container 1a side, the lid portion 1b can be fitted. It can be attached to the container 1a. Further, the holding member 16 is provided with an air hole 7 for discharging gas to the outside. A filter for separating gas and liquid is provided at one end of the opening of the air hole 7.
  • the working electrode 4 is made of a conductive material such as gold or platinum, and in the present embodiment, as shown in FIGS. 2 and 3, it has a rod shape, and one end thereof is shown in FIG. As described above, the holding member 16 is arranged so as to slightly protrude from the tip surface 10. Further, the surface of the working electrode 4 is provided with minute irregularities (not shown).
  • the counter electrode 5 is made of a conductive material such as platinum or silver-silver chloride (Ag / AgCl), and in the present embodiment, it is configured to have a linear shape.
  • the working electrode 4 and the counter electrode 5 are connected via a conducting wire 8, and a voltage is applied via the conducting wire 8 from an external power supply means (not shown). Further, the lead wire 8 is provided with an ammeter 9 for detecting the current flowing through the lead wire 8. The lead wire 8 and the ammeter 9 may be provided outside the lid portion 1b.
  • the internal liquid 13 is housed in the space formed between the lid portion 1b and the container 1a in a state where the lid portion 1b is attached to the container 1a.
  • the internal liquid 13 uses a buffer solution having a buffering action against the hydrogen ion concentration, and does not contain a substance that reacts with peracetic acid.
  • the internal liquid 13 is composed of only a buffer solution.
  • the buffer solution is not particularly limited as long as it is a buffer solution, and an acidic buffer solution, a neutral buffer solution, an alkaline buffer solution and the like can be used, but more preferably an acidic buffer solution and a neutral buffer solution are used. it can.
  • a phosphate buffer solution, an acetate buffer solution, a tris, a boric acid buffer solution, a citrate buffer solution and the like can be used.
  • An interlayer film 12 having a wettability with respect to the internal liquid 13 is laminated on the diaphragm 11 arranged inside the container 1a.
  • the interlayer film 12 is arranged so as to be sandwiched between the diaphragm 11 and the working electrode 4 with the container 1a attached to the lid portion 1b, and the working electrode 4 comes into contact with the diaphragm 11 via the interlayer film 12.
  • the wettability means that there is an affinity between the intermediate film 12 and the internal liquid 13, the internal liquid 13 stays in the intermediate film 12, wets the intermediate film 12, and the internal liquid is on the surface of the intermediate film 12. It is shown that it has a property of forming a liquid layer according to 13.
  • the film thickness of the interlayer film 12 one having a film thickness of 1 ⁇ m to 200 ⁇ m can be used.
  • a material having an elastic modulus larger than the elastic modulus of the diaphragm 11 can be used, for example, a material composed of a polymer or the like, particularly polyimide, polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • a mixed resin in which polyethylene and polyimide are mixed, polyimide, cellulose and the like can be used.
  • the interlayer film 12 is composed of a porous film in which innumerable pores 12a having a pore size of 0.05 ⁇ m to 100 ⁇ m, which are sufficiently smaller than the size of bubbles (500 ⁇ m or more) such as oxygen, are provided.
  • a protective film 17 is laminated on the diaphragm 11 arranged on the outside of the container 1a, avoiding the region where the diaphragm 11 contacts the interlayer film 12.
  • the material constituting the protective film 17 is not particularly limited, and for example, polypropylene, PFA, PET and the like can be used. It is desirable that the protective film 17 has a relatively high hardness.
  • the peracetic acid concentration meter includes a catalyst for decomposing the peracetic acid in the internal liquid.
  • catalase which is an enzyme that decomposes hydrogen peroxide
  • the concentration of catalase in the internal liquid may be in the range of 0.01 U / mg or more and 50 U / mg or less in terms of activity value, and is preferably 0.1 U / mg or more and 5 U / mg or less.
  • 1U is a unit representing the amount of catalase that decomposes 1 micromol of hydrogen peroxide per minute at 25 ° C. Since catalase in the internal liquid is an enzyme, it is possible that the catalytic activity may decrease depending on the usage environment and the like. In such a case, the internal fluid may be replaced with a new one, or the internal fluid may be replenished with new catalase.
  • the operation of the peracetic acid concentration meter 1 of the present invention having the above-described configuration will be described below.
  • the working electrode 4 comes into contact with the diaphragm 11 via the interlayer film 12, as shown in FIG. Specifically, since the working pole 4 is arranged so as to protrude from the tip surface 10, the working pole 4 comes into press contact with the diaphragm 11 via the interlayer film 12.
  • the internal liquid 13 is sealed between the container 1a and the lid portion 1b. As shown in FIG. 4, the enclosed internal liquid 13 penetrates into a minute gap between the diaphragm 11 and the intermediate film 12 and a minute gap between the intermediate film 12 and the working electrode 4.
  • the interlayer film 12 has a wettability with respect to the internal liquid 13
  • a liquid layer of the internal liquid 13 is formed on the surface of the interlayer film 12.
  • the intermediate film 12 is a porous film
  • the internal liquid 13 invades the inside of the intermediate film 12 from the pores 12a provided in the intermediate film 12. Therefore, the working electrode 4 contacts the interlayer film 12 via this liquid layer, and the intermediate film 12 also contacts the diaphragm 11 via the liquid layer.
  • the liquid layer described above is a very thin layer, it acts.
  • the pole 4 can be considered to be in contact with the diaphragm 11 substantially via the interlayer membrane 12.
  • the peracetic acid contained in the sample solution permeates the diaphragm 11, and the peracetic acid permeating the diaphragm 11 is formed between the container 1a and the lid portion 1b. It dissolves in the internal solution 13 contained in the space. Then, when a voltage is applied between the working electrode 4 and the counter electrode 5 from a power supply means (not shown) via the lead wire 8, peracetic acid undergoes a redox reaction on the surface of the working electrode 4 and on the surface of the counter electrode 5. A redox reaction occurs. Since a current flows through the lead wire 8 by these reactions, peracetic acid can be detected by measuring this current value with an ammeter 9.
  • the connector portion 6 of the peracetic acid concentration meter 1 is connected to an external device via a cable or the like, an output signal indicating the current value measured by the ammeter 9 is transmitted to the external device, and the external device transmits the output signal.
  • the concentration of peracetic acid can also be calculated.
  • the internal liquid 13 contains a catalyst that decomposes hydrogen peroxide, even if hydrogen peroxide permeates through the diaphragm 11 together with peracetic acid and dissolves in the internal liquid 13, the hydrogen peroxide in the internal liquid 13 is dissolved. It can be disassembled and reduced. As a result, the measurement error due to the reaction of hydrogen peroxide on the surface of the working electrode 4 can be reduced, and the peracetic acid concentration can be measured accurately.
  • catalase which is an enzyme, is used as the catalyst, only hydrogen peroxide contained in the internal liquid can be more selectively decomposed as compared with the case where other catalysts are used. ..
  • the peracetic acid contained in the sample solution is used. Since it does not react with the buffer solution, the concentration of peracetic acid in the sample solution does not decrease, and the disinfectant / sterilizing action of the sample solution can be maintained. Further, as described above, catalase contained as a catalyst in the internal solution selectively decomposes only hydrogen peroxide, so that even if the internal solution leaks to the sample solution side, the peracetic acid in the sample solution remains. The concentration does not decrease.
  • the buffer solution does not have persistence like iodine and bromine and catalase contained as a catalyst is not toxic, it is assumed that the internal solution 13 leaks into the sample solution used in the medical field and the food field. However, the effect on the living body can be prevented. In addition, since the buffer solution does not generate a toxic gas like bromine, the psychological burden on the operator can be reduced.
  • acetic acid in the sample solution is changed to acetic acid on the surface of the working electrode 4 by the above reaction, acetic acid may increase in the internal liquid 13 as the reaction proceeds, and the internal liquid 13 may shift to acidic.
  • the internal solution 13 of the present embodiment is composed of a buffer solution, it is possible to prevent the internal solution 13 from shifting to acidity.
  • the interlayer film 12 has a wettability with respect to the internal liquid 13, and a liquid layer formed by the internal liquid 13 is formed on the surface of the intermediate membrane 12, so that the internal liquid is formed on the surface of the working electrode 4 from this liquid layer. A specific substance dissolved in 13 can be supplied.
  • the distance between the diaphragm 11 and the working electrode 4 is increased to improve the responsiveness of the sensor, and the reaction on the surface of the working pole 4 is prevented from being hindered to prevent the sensitivity of the sensor from deteriorating. be able to.
  • the surface of the working electrode 4 is provided with minute irregularities, and the specific surface area in contact with the internal liquid 13 is increased due to these minute irregularities, so that the responsiveness of the reaction on the surface of the working electrode 4 can be improved. It can be improved further.
  • the internal liquid 13 in which the specific substance is dissolved passes through the pores 12a provided in the interlayer film 12 and is supplied to the surface of the working electrode 4, until the specific substance reaches the surface of the working electrode 4.
  • the distance can be further shortened, and the responsiveness on the surface of the working electrode 4 can be further improved.
  • the internal liquid 13 can be supplied to the surface of the working electrode 4 through the pores 12a, a specific substance can be detected stably.
  • the pore diameter of the pores 12a of the porous membrane is 0.05 ⁇ m to 100 ⁇ m, even if bubbles are generated in the sensor, the bubbles are sufficiently larger than the pores 12a and are in the pores 12a. Does not remain in. Therefore, the internal liquid 13 can be supplied to the surface of the working electrode 4 through the pores 12a without being hindered by the bubbles, so that deterioration of the sensitivity of the sensor can be prevented.
  • the elastic modulus (bulk modulus) of the interlayer film 12 is larger than the elastic modulus of the diaphragm 11, it is less likely to be deformed than the diaphragm 11, and the interlayer film 12 itself. However, it is possible to surely prevent the contact with the surface of the working pole 4 and improve the responsiveness at the working pole 4.
  • the distance between the working pole 4 and the diaphragm 11 can be further shortened, and the responsiveness on the surface of the working pole 4 is further improved. can do.
  • the holding member 16 is provided with the air hole 7, the internal pressure applied when the lid portion 1b is attached to the container 1a can be released from the air hole 7, and as described above, the inside of the sensor Even when bubbles (gas) are generated, the bubbles can be released from the air holes 7 to prevent the sensor from malfunctioning.
  • the protective film 17 since the protective film 17 is provided on the surface of the diaphragm 11 in contact with the sample solution so as to exclude the region where the diaphragm 11 contacts the interlayer film 12, the protective film 17 prevents the diaphragm 11 from being damaged. It is possible to prevent the internal liquid 13 from leaking to the sample solution side. Since the protective film 17 has a relatively high hardness, damage to the diaphragm 11 can be prevented more reliably. Further, it is possible to prevent impurities and the like in the sample solution from entering the internal liquid 13 through the diaphragm 11, and the detection accuracy can be improved.
  • the responsiveness of the working electrode 4 can be further improved by using the interlayer film 12 made of a polymer or the like, particularly polycarbonate.
  • the catalyst is not limited to the above-mentioned catalase, and may be any catalyst that promotes the decomposition of hydrogen peroxide and does not decompose peracetic acid.
  • the catalyst may be a noble metal such as platinum, platinum alloy, or titanium.
  • the precious metal described above may be present in the internal liquid. Therefore, the shape of these noble metals and the method of attaching them to the peracetic acid concentration meter 1 are not particularly limited, and for example, these noble metals formed into a rod shape or a plate shape may be immersed in the internal liquid.
  • the internal solution 13 becomes contaminated by the growth of microorganisms, and the reaction of peracetic acid on the surface of the working electrode 4 is inhibited or measured. There is a risk that the result will be inaccurate.
  • irradiation with ultraviolet rays can be mentioned.
  • the light source L1 is arranged inside a casing that houses an internal liquid such as a container 1a or a lid 1b so that the internal liquid is irradiated with ultraviolet rays, the ultraviolet rays from the light source L1 are directly inside.
  • the liquid can be irradiated.
  • Ultraviolet rays decompose hydrogen peroxide in the internal liquid to generate hydroxyl radicals, and these hydroxyl radicals can suppress the growth of microorganisms in the internal liquid. Hydroxyl radicals can also decompose organic substances that cause contamination of the working electrode.
  • Examples of the light source L1 include an ultraviolet LED and the like. For example, as shown in FIG. 8, if a wireless power supply type LED or the like is used, the light source L1 can be arranged inside the casing with a simple configuration without worrying about wiring or the like.
  • a preservative for example, sodium citrate, potassium citrate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, sodium nitrite, sodium nitrite and the like may be used, and silver, copper and zinc.
  • Metal ions such as, natural components extracted from plants and the like can be mentioned.
  • a casing for containing the internal liquid such as the container 1a and the lid 1b.
  • a material containing an antibacterial component may be used.
  • the antibacterial component include, but are not limited to, metals such as silver, copper, and zinc, and natural antibacterial components extracted from plants.
  • the peracetic acid permeation is inhibited by the adhesion of stains such as organic substances derived from the sample solution to the surface of the diaphragm 11 in contact with the sample solution, and the propagation of microorganisms to form a film.
  • the conductive mesh layer 18 may be laminated on the surface of the diaphragm 11 on the side in contact with the sample solution. Examples of the conductive mesh layer 18 include a mesh-shaped metal sheet having an opening degree that does not hinder peracetic acid permeation through the diaphragm.
  • the material of the conductive mesh layer 18 may be any material having conductivity, and is not particularly limited, but it is preferable to use a material such as silver or SUS. If silver, SUS, or the like is used as the material of the conductive mesh layer 18, hydrogen peroxide can be efficiently decomposed to generate hydroxyl radicals, and these hydroxyl radicals allow the growth of microorganisms on the diaphragm surface and organic substances. This is because adhesion can be suppressed.
  • irradiation of the diaphragm 11 with ultraviolet rays can be mentioned as a method of suppressing stains on the surface of the diaphragm 11 in contact with the sample solution and the growth of microorganisms.
  • the light source L2 for irradiating the diaphragm with ultraviolet rays may be the same as the light source L1 for irradiating the internal liquid with ultraviolet rays, or the surface of the diaphragm 11 on the side in contact with the sample solution is irradiated with ultraviolet rays from the outside.
  • the light source L2 may be provided separately.
  • the light source L2 may be attached to the casing described above, or may be independently provided outside the peracetic acid densitometer, for example, as shown in FIG.
  • the above-mentioned peracetic acid concentration meter 1 may be used in a batch-type measurement method such as immersing in a sample solution stored in a sample container such as a beaker to measure the peracetic acid concentration, or the peracetic acid concentration meter 1 may be used.
  • a sample may be supplied to the arranged flow path and used by incorporating it into the peracetic acid concentration measuring device 100 for continuously or intermittently measuring the peracetic acid concentration.
  • the peracetic acid concentration measuring device 100 for continuously or intermittently measuring the peracetic acid concentration for example, as shown in FIG. 6, the peracetic acid concentration meter 1 as described above and the peracetic acid concentration meter 1 are used.
  • a sample supply stream that separates a sample solution to be measured from a measurement cell 19 housed inside and a production line (not shown) that uses peracetic acid in the measurement cell 19, and supplies the sample solution to the measurement cell 19.
  • a path 20 and a sample lead-out flow path 21 for leading out a sample solution from the measurement cell 19 can be mentioned.
  • the peracetic acid that has passed through the diaphragm 11 and dissolved in the internal liquid at the time of measurement reacts on the surface of the working electrode 4 and is gradually decomposed, but is decomposed in the internal liquid 13.
  • Peracetic acid that has not been used may remain. If the measurement is continuously continued with the peracetic acid remaining in the internal liquid 13, there is a problem that the sensitivity of the sensor changes and that it takes time for the measurement current to stabilize. As a result, the peracetic acid concentration may not be measured accurately.
  • the peracetic acid concentration measuring device 100 supplies the zero water supply flow path 22 that further supplies a liquid containing no peracetic acid (hereinafter, also referred to as zero water) to the measuring cell 19, and zero water in the measuring cell 19.
  • a supply switching mechanism 23 that is switchably connected to the supply flow path 22 or the sample supply flow path 20 may be further provided.
  • the flow path connected to the measurement cell 19 is switched from the sample supply flow path 20 to the zero water supply flow path 22.
  • Zero water may be supplied to the diaphragm 11 of the peracetic acid concentration meter 1 in the measurement cell for a predetermined time.
  • the switching mechanism 23 switches between a supply switching valve 23V such as a three-way valve and a supply switching valve 23V for switchably connecting the sample supply flow path 20 or the zero water supply flow path 22 and the measurement cell 19. It is provided with a supply switching control unit that outputs a command signal such as timing.
  • the information processing circuit included in the peracetic acid concentration measuring device 100 fulfills the function of the supply switching control unit, for example.
  • the information processing circuit includes, for example, a digital circuit including a CPU, a memory, a communication circuit, etc. (not shown) and an analog circuit including an amplifier, an AD converter, and the like. Then, this one exerts a function as the supply switching control unit by cooperating with the CPU and its peripheral circuits according to a program stored in the memory in advance.
  • This information processing circuit may be provided in the above-mentioned external device that calculates the peracetic acid concentration based on the output signal from the ammeter 9.
  • the zero water may be a liquid that does not substantially contain peracetic acid (peracetic acid concentration is 100 ppm or less), and is preferably a liquid that does not contain peracetic acid at all, such as pure water or tap water.
  • the timing of supplying zero water and the time of supplying zero water can be appropriately changed depending on the purpose of measurement, etc., but it is preferable to continuously supply zero water for 5 minutes or more, and to supply zero water for 15 minutes or more. It is more preferable to supply.
  • Zero water can also be supplied by not supplying the sample solution to the measurement cell, discharging the sample solution in the measurement cell, and making the diaphragm of the peracetic acid concentration meter non-contact with the sample solution. You can get the same effect as. In this case, in order to replace the inside of the measurement cell for removing the sample solution adhering to the diaphragm with a gas containing no peracetic acid, a gas containing no peracetic acid may be supplied from the zero water supply channel. Good.
  • the peracetic acid enters the internal liquid 13 through the diaphragm 11 while the zero water is being supplied. Since it does not come, if the peracetic acid remaining in the internal liquid 13 is decomposed by the reaction on the surface of the working electrode 4 in this state, the concentration of the peracetic acid remaining in the internal liquid 13 can be reduced. At this time, if there is a catalyst that decomposes hydrogen peroxide in the internal liquid 13 as described above, the hydrogen peroxide generated by the decomposition of peracetic acid can be quickly decomposed, so that more peracetic acid can be decomposed. The decomposition efficiency of hydrogen peroxide can be improved.
  • the sample lead-out flow path 21 of the peracetic acid concentration measuring device 100 described above may be connected to a production line or the like for reuse of the sample solution after measurement.
  • a discharge flow path 24 and a discharge switching mechanism 25 branching from the sample lead-out flow path 21 may be further provided. ..
  • the discharge switching mechanism 25 includes, for example, a discharge switching valve 25V such as a three-way valve and a discharge switching control unit that controls the discharge switching valve 25V.
  • the information processing circuit described above fulfills the function of the discharge switching control unit, for example.
  • the discharge flow path It is not necessary to provide 24 and the discharge switching mechanism 25.
  • the sample supply flow path 20 and the zero water supply flow path 22 are connected to the measurement cell 19 via the same pipe, but the sample supply flow path 20 and the zero water supply flow path 22 are completely mutually complete.
  • Independent tubes may be used, and the flow paths 20 and 22 may be connected to the measurement cell from different directions.
  • the discharge flow path 24 may not be branched from the sample lead-out flow path 21, but may be provided independently as a flow path completely separate from the sample lead-out flow path 21.
  • the tip portion of the container 1a described above may cover the diaphragm 11 as a protective member so as to avoid the region where the diaphragm 11 contacts the interlayer film 12. ..
  • the internal solution is a buffer solution that does not react with peracetic acid, but the internal solution may be a diaphragm-type peracetic acid concentration meter containing iodine ions and bromide ions.
  • the peracetic acid concentration meter has the same shape and has a peracetic acid concentration meter having a catalyst in the internal liquid (Example 1) and a peracetic acid concentration meter having no catalyst in the internal liquid (Comparative Example 1). ) And the peracetic acid concentration was measured, and the measurement error of each was investigated.
  • Example 1 a peracetic acid densitometer containing catalase in the internal liquid, which was described in detail in the above embodiment, was used.
  • a phosphate buffer solution (pH 7.0) in which KCl was dissolved so as to be 1 mol / L was used as the internal solution, and catalase was added so as to be 0.2 U / mg.
  • a sample solution containing peracetic acid but not hydrogen peroxide and a sample solution containing peracetic acid and hydrogen peroxide were prepared.
  • a sample solution containing peracetic acid and hydrogen peroxide a sample solution in which the hydrogen peroxide concentration was variously changed in the range of 0.0% to 3.5% was prepared.
  • the peracetic acid concentration of each of these sample solutions was measured using the above-mentioned peracetic acid concentration meter.
  • the peracetic acid concentration of the same sample solution as that measured by the peracetic acid concentration meter was measured in parallel by the titration method.
  • the difference between the concentration indicated value measured by the peracetic acid densitometer and the concentration indicated value measured by the titration method for accurately measuring the peracetic acid concentration by neutralization titration was defined as the measurement error.
  • the peracetic acid concentration was measured by the titration method using COM-1700 manufactured by Hiranuma Sangyo. The experiment was performed twice.
  • the results of the first time are shown in FIG. 7 (a), and the results of the second time are shown in FIG. 7 (b).
  • the vertical axis of the graph of FIG. 7 represents the measurement error
  • the horizontal axis represents the concentration of hydrogen peroxide contained in the sample solution.
  • Comparative Example 1 In Comparative Example 1, the same peracetic acid concentration meter as that used in Example 1 was used except that the internal solution did not contain catalase. The measurement error was calculated by the same procedure as in Example 1. The experiment was performed twice. The results of the first time are shown in FIG. 7 (a), and the results of the second time are shown in FIG. 7 (b).
  • the peracetic acid concentration of the sample solution containing hydrogen peroxide can be determined as compared with the case without a catalyst. It was found that the measurement error when measuring can be significantly reduced.
  • the error in the peracetic acid concentration measurement can be suppressed to a small value, and the peracetic acid concentration can be measured more accurately than before.

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Abstract

L'invention concerne un dispositif de mesure de la concentration d'acide peracétique avec lequel il est possible de mesurer avec précision la concentration d'acide peracétique tout en réduisant au minimum les erreurs dues au peroxyde d'hydrogène. Ce dispositif de mesure de la concentration d'acide peracétique est du type à diaphragme pour mesurer la concentration en acide peracétique dans une solution d'échantillon, et est caractérisé en ce qu'il est équipé des éléments suivants : un diaphragme perméable à l'acide peracétique ; un liquide interne dans lequel est dissous l'acide peracétique ayant traversé le diaphragme ; une électrode de travail et une contre-électrode immergées dans le liquide interne ; et un catalyseur servant à décomposer le peroxyde d'hydrogène présent dans le liquide interne.
PCT/JP2020/030656 2019-08-28 2020-08-12 Dispositif de mesure de concentration d'acide peracétique WO2021039392A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024111582A1 (fr) * 2022-11-22 2024-05-30 オリンパス株式会社 Procédé d'étalonnage de dispositif de mesure d'acide peracétique et système d'étalonnage d'appareil de dosage d'acide peracétique

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS593345A (ja) * 1982-06-30 1984-01-10 Hitachi Ltd 妨害成分除去用電極を装備した溶存酸素計
JPH0445798A (ja) * 1990-06-08 1992-02-14 Hiranuma Sangyo Kk 過酸化水素と過酢酸の分別測定方法
JPH04346063A (ja) * 1991-05-24 1992-12-01 Hitachi Ltd 酸素センサ及びこれを用いた分析装置
US5770039A (en) * 1996-05-03 1998-06-23 Ecolab Inc. Method and apparatus for measuring and controlling active oxygen concentration in a bleach environment
JP2001235443A (ja) * 2000-02-22 2001-08-31 Matsushita Electric Ind Co Ltd ｐＨセンサー及びそれを備えたイオン水生成器
JP2006078260A (ja) * 2004-09-08 2006-03-23 Horiba Ltd 残留塩素計とそれを用いた給水端末モニタ
JP2008026313A (ja) * 2006-06-21 2008-02-07 Horiba Ltd 比較電極、複合電極
JP2009069025A (ja) * 2007-09-13 2009-04-02 Dkk Toa Corp 隔膜式過酸化水素電極
JP2015230172A (ja) * 2014-06-03 2015-12-21 株式会社 堀場アドバンスドテクノ 隔膜式センサ、液体分析計
JP2015230173A (ja) * 2014-06-03 2015-12-21 株式会社 堀場アドバンスドテクノ 過酢酸濃度計

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4346063B2 (ja) 2002-12-03 2009-10-14 大日本印刷株式会社 転写マスクブランク、転写マスク並びにその転写マスクを用いた転写方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS593345A (ja) * 1982-06-30 1984-01-10 Hitachi Ltd 妨害成分除去用電極を装備した溶存酸素計
JPH0445798A (ja) * 1990-06-08 1992-02-14 Hiranuma Sangyo Kk 過酸化水素と過酢酸の分別測定方法
JPH04346063A (ja) * 1991-05-24 1992-12-01 Hitachi Ltd 酸素センサ及びこれを用いた分析装置
US5770039A (en) * 1996-05-03 1998-06-23 Ecolab Inc. Method and apparatus for measuring and controlling active oxygen concentration in a bleach environment
JP2001235443A (ja) * 2000-02-22 2001-08-31 Matsushita Electric Ind Co Ltd ｐＨセンサー及びそれを備えたイオン水生成器
JP2006078260A (ja) * 2004-09-08 2006-03-23 Horiba Ltd 残留塩素計とそれを用いた給水端末モニタ
JP2008026313A (ja) * 2006-06-21 2008-02-07 Horiba Ltd 比較電極、複合電極
JP2009069025A (ja) * 2007-09-13 2009-04-02 Dkk Toa Corp 隔膜式過酸化水素電極
JP2015230172A (ja) * 2014-06-03 2015-12-21 株式会社 堀場アドバンスドテクノ 隔膜式センサ、液体分析計
JP2015230173A (ja) * 2014-06-03 2015-12-21 株式会社 堀場アドバンスドテクノ 過酢酸濃度計

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024111582A1 (fr) * 2022-11-22 2024-05-30 オリンパス株式会社 Procédé d'étalonnage de dispositif de mesure d'acide peracétique et système d'étalonnage d'appareil de dosage d'acide peracétique

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