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WO2019078265A1 - Dispositif d'analyse et dispositif de mesure de carbone organique total - Google Patents

Dispositif d'analyse et dispositif de mesure de carbone organique total Download PDF

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Publication number
WO2019078265A1
WO2019078265A1 PCT/JP2018/038692 JP2018038692W WO2019078265A1 WO 2019078265 A1 WO2019078265 A1 WO 2019078265A1 JP 2018038692 W JP2018038692 W JP 2018038692W WO 2019078265 A1 WO2019078265 A1 WO 2019078265A1
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WO
WIPO (PCT)
Prior art keywords
hole
diameter
heating furnace
seal member
combustion tube
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2018/038692
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English (en)
Japanese (ja)
Inventor
中森　明興
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shimadzu Corp
Original Assignee
Shimadzu Corp
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 Shimadzu Corp filed Critical Shimadzu Corp
Priority to JP2019549322A priority Critical patent/JP6879377B2/ja
Publication of WO2019078265A1 publication Critical patent/WO2019078265A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • G01N31/12—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion

Definitions

  • the present invention is an analyzer equipped with a heating furnace for heating a combustion tube into which a sample is introduced, thereby burning and oxidizing the sample, and an all-organic carbon measuring apparatus equipped with the analyzer. About.
  • TOC total organic carbon
  • TN total nitrogen
  • the collected sample is introduced into the combustion unit, and in the all-organic carbon measuring device, the carbon component in the sample is burned, oxidized and decomposed to be carbon dioxide, and in the total nitrogen measuring device, the sample is The nitrogen components of the catalyst are burned and oxidized to be converted to nitrogen oxide (NO), and a gas containing them is introduced into the cell of the detection unit.
  • NO nitrogen oxide
  • the detection unit of the water quality analyzer will be described.
  • the absorbance derived from the carbon dioxide concentration in the gas introduced to the cell is measured.
  • the total nitrogen measuring device the amount of luminescence derived from the nitrogen oxide concentration in the gas led to the cell is measured.
  • the peak area value of the detection signal data obtained by these measurements total organic carbon or total nitrogen in the sample is quantified. That is, in order to quantify total organic carbon or total nitrogen, a calibration curve indicating the relationship between total organic carbon or total nitrogen and the area value of the peak of the detection signal data is prepared in advance, and the measured is measured. Based on the calibration curve, total organic carbon or total nitrogen can be quantified from the area value of the peak according to the signal data (see Patent Document 1).
  • a combustion unit into which the collected sample is introduced is disposed in the heating furnace.
  • the sample is heated to 680 ° C. by a heating furnace in the presence of abundant purified air in a combustion tube filled with a platinum catalyst.
  • the outer periphery of the heating furnace may be surrounded by an outer wall of a heat insulating material mainly composed of ceramic fibers or alumina fibers so that heating of the combustion tube by the heating furnace is performed efficiently and uniformly (Patent Document 2) reference).
  • the outer periphery of the heating furnace is surrounded by the outer wall made of a heat insulating material, heat can be prevented from escaping from the outer periphery of the heating furnace.
  • the heat insulating performance can be maintained relatively by covering the upper part of the casing of the heating furnace with a ceramic member (a lid or the like) having a hole through which the combustion tube main body can be inserted.
  • a ceramic member a lid or the like
  • the outlet portion of the combustion tube is generally a thin tube portion for catalyst holding and piping connection, which causes a large gap with the hole.
  • the lower portion of the casing of the heating furnace is provided with a hole of a larger diameter than the outer diameter of the combustion tube main body. The reason for this is to be able to be pulled out when the combustion tube main body is broken inside the furnace. Therefore, this structure can not be avoided for maintenance.
  • the analyzer concerning the 1st mode of the present invention is provided with the heating furnace which heats a combustion pipe, in order to burn and oxidize and decompose the sample introduced into the combustion pipe,
  • the case In the lower part of the case of the furnace, the case is penetrated and a hole with a diameter larger than the outer diameter of the combustion tube main body is bored, and heat insulation having a hole into which the thin tube part at the outlet of the combustion tube main body is inserted
  • a sealing member made of a material is attached to a hole in a lower portion of a casing of a heating furnace to seal the flow of heat.
  • ceramic-made is suitable.
  • casing lower part of a heating furnace is suitable.
  • the seal member may be provided with flanges having a diameter smaller than the diameter of the hole and larger than the diameter of the hole at both ends of the body longer than the lower housing thickness of the heating furnace.
  • the portion may have a hole into which the thin tube portion of the outlet portion of the combustion tube main body is inserted, and a tapered portion may be formed from the upper flange portion toward the body portion, and the seal member is in the axial direction May be divided into at least two.
  • the flange portion above the seal member has a function to prevent the seal member from falling from the hole when the seal member is mounted in the hole formed in the lower portion of the casing of the heating furnace.
  • the seal member is divided in the axial direction allows the seal member (upper flange portion) having a flange portion with a diameter larger than the diameter of the hole portion to be inserted into the heating furnace from the hole portion.
  • the present invention is not limited to two divisions.
  • the center of gravity moves to the upper side (inner side of the heating furnace) of the seal member, and when the seal member is pushed upward from below, the difference between the outer diameter of the body portion and the diameter of the hole portion
  • the presence of the (gap) allows the seal member to spread outward (left and right in the case of two divisions), and helps the left and right weight balance to easily spread laterally.
  • the large diameter side of the tapered portion may be equal to or less than or equal to the diameter of the hole in the hole.
  • the large diameter side of the tapered portion preferably has a diameter substantially equal to the diameter of the hole, but the category including the diameter equal to or less than the diameter of the hole includes the diameter of the trunk as the minimum diameter. That is, when the large diameter side of the tapered portion has the same diameter as the diameter of the body portion, the tapered portion substantially does not exist, but the present invention also includes this.
  • the combustion tube is a reaction unit that burns, oxidizes and decomposes the carbon component in the sample to convert it to carbon dioxide, and light is transmitted to the cell and the cell that circulates the gas from the reaction unit.
  • It is a total organic carbon measuring apparatus provided with the measurement part which has a light source which irradiates, and a detector which detects the light which permeate
  • the lower portion of the casing of the heating furnace is a seal member made of a heat insulating material having a hole at its central portion for inserting and holding a thin tube portion at the outlet of the combustion tube main body.
  • the heat exchanger can be effectively thermally insulated simply by installing the combustion pipe in the heating furnace, since it is mounted in the hole of the housing to seal the heat outflow. Further, since the thin tube portion at the outlet of the combustion tube main body is held by the lower housing of the heating furnace via the seal member, it can be stably attached in the heating furnace.
  • the seal member can be easily attached from the hole bored in the lower portion of the casing of the heating furnace. It can be easily performed only by pushing up the seal member upward (inside the heating furnace) in inserting the hole into the hole in the center part. Therefore, the variation at the time of attachment of the combustion pipe in a heating furnace by a worker can be eliminated, and stable measurement of total organic carbon etc. becomes possible.
  • the all-organic carbon measuring apparatus 11 supplies a carrier gas to send a carrier gas to the all-organic carbon measuring unit 12 and the combustion tube 14 of the oxidation reaction unit 13 provided in the all-organic carbon measuring unit 12. And a multiport valve 16 for switching them.
  • a sampling syringe 17 for measuring and collecting sample water is connected to a common port of the multiport valve 16.
  • other ports include 1) a sample introduction unit, 2) hydrochloric acid used when removing inorganic carbon components from sample water, 3) dilution water, and 4) inorganic carbon reaction unit 18 5)
  • the drain drain ports are connected to one another.
  • the total organic carbon measurement apparatus 11 is configured to be able to inject the sample collected from the autosampler 19 into the combustion pipe 14 of the total organic carbon measurement unit 12.
  • An exemplary volume of the sampling syringe 17 is around 5 mL.
  • a vent gas inlet (not shown) for introducing a carrier gas is provided.
  • the vent gas inlet is connected to the carrier gas supply unit 15 via the solenoid valve 20.
  • the gas venting mechanism is realized by the sampling syringe 17.
  • the carrier gas supply unit 15 is configured to supply high purity air as a carrier gas.
  • the carrier gas supply unit 15 includes, in order from the upstream side, a carrier gas inlet, a solenoid valve, a pressure regulating valve that regulates pressure, a pressure gauge that measures pressure, a mass flow controller that regulates flow, a flow meter, And the humidifier is connected.
  • the carrier gas whose flow rate is measured and humidified is sent to the combustion tube 14. Further, the carrier gas whose flow rate is adjusted for humidification is also supplied to the sampling syringe 17 as a ventilation gas through the solenoid valve 20.
  • the combustion tube 14 of the oxidation reaction unit 13 includes a sample injection unit 21 at the top.
  • a thin tube portion 14 a is provided at the outlet of the combustion tube 14 main body.
  • An oxidation catalyst for converting all of the carbon components in the sample into carbon dioxide is held at the inlet of the thin tube portion 14a.
  • the oxidation catalyst may contain a metal oxide or a noble metal.
  • the combustion tube 14 is inserted into the heating furnace 22 and heated to 680 ° C., for example.
  • the carrier gas supply unit 15 is connected to the sample injection unit 21 via a check valve (not shown) that prevents backflow of the carrier gas.
  • the narrow tube portion 14 a of the combustion tube 14 main body is connected to the carrier gas inlet of the inorganic carbon reaction unit 18 via the cooling unit 23 and the backflow prevention trap 24.
  • the inorganic carbon reaction unit 18 when measuring inorganic carbon, phosphoric acid is supplied as an inorganic carbon reaction liquid by an optional means such as a pump, and the sample water is supplied to the inorganic carbon reaction unit 18 as a multiport valve. Direct injection is performed by the switching of 16 and the operation of the sampling syringe 17. In the injected sample water, inorganic carbon is generated as carbon dioxide, and the carbon dioxide is led to the dehumidifying electron cooler 25.
  • the inorganic carbon reaction liquid of the inorganic carbon reaction unit 18 is discharged from a drain solenoid valve (not shown).
  • the gas passed through the dehumidifying electron cooler 25 is not shown as a non-dispersive infrared analysis method (NDIR) via a dehumidifier for removing water or a membrane filter (for removing a halogen scrubber and foreign matter).
  • NDIR non-dispersive infrared analysis method
  • the measurement unit 26 includes a cell in which a light source and a detector are disposed opposite to each other. The intensity of the detector output signal corresponds to the amount of total carbon or inorganic carbon. The amount of inorganic carbon can be determined by subtracting the amount of inorganic carbon from the amount of total carbon measured in this manner.
  • the discharged carbon dioxide is adsorbed by a CO 2 absorber (not shown). Further, a drain pot (not shown) for removing water is connected to the dehumidifying electronic cooler 25.
  • the oxidation reaction unit 13 includes a heating furnace 22 and a combustion tube 14 (see FIG. 2C) attached to the inside of the heating furnace 22.
  • the lower casing 22a of the heating furnace 22 penetrates the casing 22a in the thickness direction (the thickness of the casing 22a is indicated by t in FIG. 2) and the outer diameter of the main body of the combustion tube 14 A hole 7 having a hole diameter d2 larger than d1 (see FIG. 2C) is provided.
  • the reason for this configuration is to allow removal when the combustion tube 14 is broken inside the heating furnace 22 and is a structure that can not be avoided for maintenance.
  • the seal member 1 is mounted in a hole 7 provided in the lower housing 22 a of the heating furnace 22.
  • the seal member 1 is divided into two.
  • the seal member 1 has rod-shaped body portions 4a and 4b.
  • the body portions 4 a and 4 b have a diameter smaller than the diameter d 2 of the hole 7.
  • the length of the body portions 4 a and 4 b (the dimension in the thickness direction of the lower housing 22 a) is larger than the thickness of the lower housing 22 a of the heating furnace 22.
  • the flanges 2a, 2b, 3a, 3b are connected to both ends of the body 4a, 4b (in the thickness direction of the lower housing 22a).
  • the flanges 2a, 2b, 3a, 3b have a diameter d3 larger than the diameter d2 of the hole 7. .
  • a hole 6 is provided at the center of the seal member 1.
  • the hole 6 may be provided at a position deviated from the central portion of the seal member 1.
  • the narrow tube portion 14 a of the main body of the combustion tube 14 is inserted into the hole 6.
  • the upper flanges 2a, 2b are not disk-like, as shown in the top view of FIG. Thereby, the seal member 1 (upper flanges 2a and 2b) can be mounted in the heating furnace 22 from the hole 7 while maintaining the function as the flanges 2a and 2b.
  • the seal member 1 is formed with tapered portions 5a, 5b that taper from the upper flange portions 2a, 2b toward the body portions 4a, 4b.
  • the maximum diameter of the tapered portions 5a and 5b is set to the same diameter as the inner diameter d2 of the hole portion 7.
  • the minimum diameter of the tapered portions 5a, 5b is the same as the diameter of the body portions 4a, 4b.
  • the position of the smallest diameter portion in the body portions 4a and 4b is desirably equal to or less than the upper one-third of the length (axial direction) of the body portions 4a and 4b.
  • the tapered portions 5 a and 5 b can position the center of gravity of the seal member 1 upward (inside the heating furnace 22).
  • FIGS. 2A to 2C an operation of attaching the combustion pipe 14 (thin tube portion 14a) to the seal member 1 will be described with reference to FIGS. 2A to 2C.
  • the lower flange portions 3a and 3b are heating furnaces from the state of FIG. 2A.
  • the seal member 1 is pushed upward into the heating furnace 22 by hand until it abuts on the lower housing 22a of 22.
  • the seal member 1 Since the seal member 1 is divided into two parts, as shown in FIG. 2B, the seal member 1 spreads to the left and right due to the difference (gap) between the outer diameter of the body 4a, 4b and the hole diameter d2 of the hole 7.
  • the center of gravity is located at the upper part by forming the tapered portions 5a and 5b. This helps the seal member 1 to spread to the left and right easily with the upper and lower weight balance.
  • a chamfered portion 8 is formed on the lower flange 3a, 3b side of the hole 6 provided in the sealing member 1. As a result, the collision of the lower flanges 3a and 3b of the seal member 1 can be alleviated, and the left and right spread can be further permitted.
  • the hand pushing up the seal member 1 while inserting the thin tube portion 14a of the combustion tube 14 from the inside of the heating furnace 22 into the hole 6 of the seal member 1 When released, the seal member 1 is fixed around the narrow tube portion 14 a and can be held by the seal member 1.
  • the seal member 1 is pushed down until the upper flanges 2a and 2b abut against the hole 7, and the taper is set such that the upper flanges 2a and 2b and the maximum diameter are the same as the inner diameter d2 of the hole 7
  • the holes 7 are sealed and thermally insulated by 5a and 5b.
  • the maximum diameters of the tapered portions 5 a and 5 b are set to the same diameter as the inner diameter d 2 of the hole 7.
  • the first aspect of the present invention is An analyzer comprising a heating furnace for heating a combustion tube into which a sample is introduced, thereby burning the sample for oxidative decomposition.
  • a thin tube portion is provided at the outlet of the combustion tube,
  • the heating furnace has a housing, The lower part of the casing of the heating furnace is provided with a hole penetrating the casing, The diameter of the hole is larger than the outer diameter of the combustion tube,
  • the hole is provided with a sealing member for sealing the hole,
  • the sealing member is made of a heat insulating material,
  • the sealing member is provided with a hole for inserting a thin tube portion of the combustion tube, It is an analyzer.
  • the seal member may have a body and a brim.
  • the body may have a diameter smaller than the diameter of the hole and may have a length larger than the thickness of the lower casing of the heating furnace.
  • the flanges may be provided at both ends of the body, The flange may have a diameter larger than the diameter of the hole,
  • the seal member may have a tapered portion formed from the flange portion toward the body portion.
  • the seal member may be divided into at least two in the axial direction. .
  • the tapered portion may have a diameter equal to or less than the diameter of the hole on the large diameter side.
  • the second aspect of the present invention is An all-organic carbon measuring apparatus comprising a measuring unit,
  • the combustion tube is a reaction unit which is disposed in the heating furnace and burns, oxidizes and decomposes a carbon component in a sample, and converts it into carbon dioxide.
  • the measuring unit is an all-organic carbon measuring apparatus having a cell for circulating the gas from the reaction unit, a light source for irradiating the cell with light, and a detector for detecting the light transmitted through the cell.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Combustion & Propulsion (AREA)
  • Engineering & Computer Science (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

La présente invention concerne un dispositif d'analyse comprenant un four de chauffage permettant de chauffer un tube de combustion dans lequel un échantillon est introduit et ainsi de brûler l'échantillon et d'effectuer une décomposition d'oxydation. Une petite partie de tube est placée sur une sortie du tube de combustion. Le four de chauffage comprend un boîtier. Une partie trou qui traverse le boîtier du four de chauffage est située dans une partie inférieure du boîtier. Le diamètre de la partie trou est supérieur au diamètre extérieur du tube de combustion. Un matériau d'étanchéité qui scelle la partie trou est disposé dans la partie trou. Un trou d'insertion de la petite partie de tube du tube de combustion est disposée dans le matériau d'étanchéité.
PCT/JP2018/038692 2017-10-18 2018-10-17 Dispositif d'analyse et dispositif de mesure de carbone organique total Ceased WO2019078265A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019549322A JP6879377B2 (ja) 2017-10-18 2018-10-17 分析装置および全有機体炭素測定装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-201448 2017-10-18
JP2017201448 2017-10-18

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WO2019078265A1 true WO2019078265A1 (fr) 2019-04-25

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PCT/JP2018/038692 Ceased WO2019078265A1 (fr) 2017-10-18 2018-10-17 Dispositif d'analyse et dispositif de mesure de carbone organique total

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JP (1) JP6879377B2 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120121856A (zh) * 2025-05-14 2025-06-10 德州市荣光生物科技有限公司 一种生物柴油燃烧性能检测设备及其使用方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012137377A (ja) * 2010-12-27 2012-07-19 Shimadzu Corp 分析装置
JP2012137459A (ja) * 2010-12-28 2012-07-19 Shimadzu Corp 電気炉を備えた分析装置
CN102778530A (zh) * 2012-08-10 2012-11-14 宇星科技发展(深圳)有限公司 一种干式氧化反应器
CN102944454A (zh) * 2012-10-23 2013-02-27 杭州泰林生物技术设备有限公司 总有机碳测定用燃烧炉

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012137377A (ja) * 2010-12-27 2012-07-19 Shimadzu Corp 分析装置
JP2012137459A (ja) * 2010-12-28 2012-07-19 Shimadzu Corp 電気炉を備えた分析装置
CN102778530A (zh) * 2012-08-10 2012-11-14 宇星科技发展(深圳)有限公司 一种干式氧化反应器
CN102944454A (zh) * 2012-10-23 2013-02-27 杭州泰林生物技术设备有限公司 总有机碳测定用燃烧炉

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120121856A (zh) * 2025-05-14 2025-06-10 德州市荣光生物科技有限公司 一种生物柴油燃烧性能检测设备及其使用方法

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JP6879377B2 (ja) 2021-06-02

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