WO2014038019A1 - ヘッドスペース試料導入装置とそれを備えたガスクロマトグラフ - Google Patents
ヘッドスペース試料導入装置とそれを備えたガスクロマトグラフ Download PDFInfo
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- WO2014038019A1 WO2014038019A1 PCT/JP2012/072635 JP2012072635W WO2014038019A1 WO 2014038019 A1 WO2014038019 A1 WO 2014038019A1 JP 2012072635 W JP2012072635 W JP 2012072635W WO 2014038019 A1 WO2014038019 A1 WO 2014038019A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/24—Automatic injection systems
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N2030/009—Extraction
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/065—Preparation using different phases to separate parts of sample
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/202—Injection using a sampling valve rotary valves
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/207—Injection using a sampling valve with metering cavity, e.g. sample loop
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
Definitions
- the present invention relates to a headspace sample introduction device that collects a gas sample volatilized from a liquid sample or a solid sample by a headspace method and introduces the sample into an analysis device such as a gas chromatograph, and an analysis device including the headspace sample introduction device.
- the present invention relates to a gas chromatograph as an example.
- the headspace method volatilizes components having a relatively low boiling point by heating a liquid sample or solid sample contained in a sample container to a certain temperature for a certain period of time, and removes the components from the headspace (upper space) in the sample container.
- a sample introduction method in which a certain amount of gas is collected and introduced into the analyzer.
- the headspace analysis method refers to analyzing by introducing a sample into the analyzer by the headspace method.
- a typical example of an analyzer for performing such a headspace analysis method is a gas chromatograph.
- sample gas is collected from the head space of the sample container into the sample loop, and the collected sample gas is introduced into the analyzer.
- a method for collecting the sample gas into the sample loop it is common to collect the sample gas into the sample loop when the pressure at the other end of the sample loop, one end of which is connected to the head space of the sample container, becomes atmospheric pressure.
- the sample component concentration is lowered and the analysis sensitivity may be insufficient.
- the object of the present invention is to make the back pressure of the sample loop constant when collecting the sample gas into the sample loop without using a flow rate adjusting valve.
- the constant pressure from the pressure source is divided downstream of the sample loop by the flow path resistance to obtain a predetermined constant pressure.
- a pressure channel is provided.
- the headspace sample introduction apparatus of the present invention includes a sample gas flow path connected to the headspace of a sample container having a headspace for collecting a sample gas generated from a sample, and a pressurized gas supply having a constant first pressure greater than atmospheric pressure.
- a first pressurized flow path connected to the source, a sample loop for collecting the sample gas, a discharge flow path for discharging the sample gas, a carrier gas flow path to which the carrier gas is supplied, and an analysis connected to the analyzer
- a flow path, a second pressurizing flow path that applies a constant pressure higher than atmospheric pressure to the discharge flow path, and a flow path switching mechanism are provided.
- the flow path switching mechanism includes a head space pressure flow path configuration that connects the first pressure flow path to the head space, a sample gas sampling flow path configuration that connects the sample loop between the sample gas flow path and the discharge flow path, and a sample. It is configured to switch between the sample gas introduction channel configurations connecting the loop between the carrier gas channel and the analysis channel.
- the second pressurizing flow path is connected to one end downstream of the discharge flow path and the other end opened to the atmosphere in order to apply a constant pressure larger than the atmospheric pressure to the discharge flow path without performing feedback control.
- a first resistance tube, and a second resistance tube having one end connected downstream of the discharge passage and the other end connected to a pressurized gas supply source having a constant second pressure greater than atmospheric pressure, Then, the second pressure is divided by the second resistance tube, and a pressure that becomes a constant pressure larger than the atmospheric pressure is applied to the discharge channel.
- the pressurized gas supply source to which the first pressurized flow path is connected and the pressurized gas supply source to which the second pressurized flow path is connected can be different pressurized gas pressure sources, or a common pressurized gas. Can be a source.
- a part of the gas supplied from the first pressurized flow path to the sample container in order to increase the pressure in the head space of the sample container is collected in the sample loop together with the sample gas, and then introduced into the analyzer together with the carrier gas. . Therefore, it is desirable that the gas supplied from the first pressurized flow path is the same as the carrier gas.
- the pressurized gas used in the second pressurized flow path is not introduced into the analyzer and need not be the same as the carrier gas.
- the gas chromatograph of one embodiment is configured such that the pressurized gas supply source to which the first pressurized channel is connected is configured to supply the same gas as the carrier gas supplied from the carrier gas channel as the pressurized gas. is there.
- the pressurized gas supply source to which the first pressurized flow path is connected and the pressurized gas supply source to which the second pressurized flow path is connected are a common pressurized gas supply source, and the carrier gas flow The same gas as the carrier gas supplied from the channel can be supplied as the pressurized gas.
- the pressurized gas supply source to which the first pressurized flow path is connected and the pressurized gas supply source to which the second pressurized flow path is connected are different pressurized gas supply sources, and the first pressurized gas supply source is connected.
- the pressurized gas supply source to which the pressure channel is connected supplies the same gas as the carrier gas supplied from the carrier gas channel as the pressurized gas, and the pressurized gas supply source to which the second pressurized channel is connected is A gas other than the carrier gas can be supplied.
- a pressure flow path is provided downstream of the sample loop by dividing the constant pressure from the pressure source by the flow path resistance to obtain a predetermined constant pressure.
- the configuration for keeping the constant is simplified. Further, since a feedback control device including a flow rate adjusting valve is not provided, a flow rate adjusting valve that is contaminated and deteriorates its performance is unnecessary, and there is no decrease in reliability due to the flow rate adjusting valve.
- FIG. 1 shows an embodiment of a sample introduction apparatus.
- the sample container 2 contains a liquid or solid sample 4 therein and generates sample gas from the sample 4 when heated.
- the sample container 2 is sealed with a septum 6, and the upper space of the sample 4 in the sample container 2 becomes a head space 3 for storing the generated sample gas.
- a septum 6 is fixed by a cap 5 so that the inside of the sample container 2 can be pressurized to a pressure larger than atmospheric pressure, for example, a pressure 50 to 200 kPa higher than atmospheric pressure.
- the sample container 2 is heated at a constant temperature for a certain time.
- the heating temperature is set according to the sample gas to be measured, and is, for example, 35 to 300 ° C.
- a sample component having a boiling point equal to or lower than the set temperature is volatilized and becomes a sample component gas, which is stored in the head space 3.
- a needle is inserted through the septum 6.
- the needle is provided at the tip of the sample gas flow path 8.
- a base end portion of the sample gas flow path 8 is connected to one port of a hexagonal valve 10 constituting a flow path switching mechanism.
- the first pressurizing flow path 12 for applying a constant pressure larger than the atmospheric pressure is connected to one port of the six-way valve 10 via an on-off valve 14 formed of a solenoid valve. ing.
- the on-off valve 14 also constitutes a flow path switching mechanism.
- a proximal end portion of the pressure channel 12 is connected to the pressure inlet 32.
- the pressure inlet 32 is a joint for pipe connection to a pressurized gas supply source.
- the sample loop 16 for collecting the sample gas is a flow path having a predetermined capacity, and is connected between the two ports of the hexagonal valve 10.
- a discharge flow path 20 is connected between the on-off valve 14 and the hexagonal valve 10 in the pressurization flow path 12 via a T-shaped joint 18.
- the discharge channel 20 has a pressure sensor (PS) 22 on the upstream side close to the joint 18, and has an open / close valve 24 formed of a solenoid valve downstream of the pressure sensor 22.
- the discharge channel 20 has a vent outlet 26 downstream from the on-off valve 24.
- One end of a resistance tube 28 is connected to the vent outlet 26, and the other end of the resistance tube 28 is open to the atmosphere.
- One end of a resistance tube 30 is further connected to the vent outlet 26, and the other end of the resistance tube 30 is connected to a pressure introduction port 32.
- the first and second resistance tubes 28 and 30 apply a constant pressure larger than the atmospheric pressure as the back pressure of the discharge channel 20 by applying a constant pressure larger than the atmospheric pressure from the pressure introduction port 32. 2 pressurizing flow paths 29 are formed.
- the other two ports of the hexagonal valve 10 are connected to a carrier gas channel 34 to which a carrier gas is supplied and an analysis channel 36 connected to the analyzer.
- the pressure inlet 32 is connected to a pressurized gas supply source, and a constant pressure larger than atmospheric pressure is applied from the pressurized gas supply source.
- the pressurized gas supply source may be any source that can supply pressurized gas at a constant pressure.
- the pressurized gas is an inert gas, preferably a carrier gas used in an analyzer.
- As the carrier gas it is appropriate to use an inert gas such as helium, argon or nitrogen.
- the pressurizing flow path 12 for pressurizing the head space is configured to pressurize the hexagonal valve 10 by supplying an inert gas from the sample gas flow path 8 through the sample loop 16 to the head space.
- the present invention is not limited to this, and the pressurized flow path 12 may be configured to supply a pressurized gas to the sample container 3 without passing through the sample loop 16.
- both the pressurized channels 12 and 29 have a common pressure inlet 32. It is connected to the.
- the pressurized gas supply sources of both of the pressurized flow paths 12 and 29 are not necessarily the same.
- FIG. 2 shows an embodiment in which the pressurized gas supply source of the pressurized flow path 12 and the pressurized gas supply source of the pressurized flow path 29 are different.
- the pressurized flow path 12 is provided with a pressure inlet 32a, and a pressurized flow is provided to connect the pressurized flow path 29 to another pressurized gas supply source.
- the passage 29 is provided with a pressure inlet 32b different from the pressure inlet 32a.
- the pressure inlets 32a and 32b are joints for pipe connection to the respective pressurized gas supply sources.
- the pressure inlet 32a is connected to the carrier gas supply mechanism of the analyzer to which the sample introduction device is connected so that the carrier gas supplied to the carrier gas channel 34 as the pressurized gas is supplied as the pressurized gas.
- the pressure inlet 32b is connected to a mechanism that pressurizes and supplies air to a constant pressure higher than atmospheric pressure so that a gas different from the carrier gas, for example, air, can be used as the pressurized gas.
- FIG. 3 shows an embodiment in which the sample introduction apparatus of FIG. 1 is connected to the gas chromatograph body 40 to constitute a gas chromatograph apparatus as a whole.
- the gas chromatograph main body 40 includes a separation column 46 to which a sample gas is supplied together with a carrier gas, and a detector (D) 50 that detects a sample component separated by the separation column 46.
- An automatic pressure control device for supplying the carrier gas at a constant pressure by the pressure inlet 32 of the pressurization channels 12 and 29 so that the carrier gas used in the gas chromatograph is used as the pressure source of the pressurization channel 12 and the pressurization channel 29. (APC) 42 is connected.
- the automatic pressure control device 42 is connected to a carrier gas supply source such as a gas cylinder, and a carrier gas adjusted to a constant pressure larger than the atmospheric pressure is supplied from the automatic pressure control device 42 as a pressurized gas.
- the automatic pressure control device 42 is provided as an attached device to the gas chromatograph main body 40, the attached automatic pressure control device 42 can be used. If there is no such attached automatic pressure control device 42, an automatic pressure control device 42 is provided separately.
- the carrier gas channel 34 of the sample introduction device is connected to an automatic flow rate control device (AFC) 44 of the gas chromatograph main body 40, and the carrier gas adjusted to a constant flow rate by the automatic flow rate control device 44 enters the carrier gas channel 34. Supplied.
- AFC automatic flow rate control device
- the analysis flow path 36 of the sample introduction device is connected to a separation column 46 of the gas chromatograph.
- the analysis flow path 36 is branched by a T-shaped joint on the upstream side of the separation column 46 and is also connected to the split flow path 48.
- the downstream end of the split flow path 48 is connected to an automatic flow control device 44 in order to keep the flow rate of the split carrier gas constant.
- the same carrier gas for example, helium, is supplied from the automatic pressure controller 42 and the automatic flow controller 44.
- FIG. 4 shows a process of heating the sample in the sample container 2 to generate volatile gas from the sample and then pressurizing the sample container 2.
- a liquid sample or a solid sample is placed as a sample in the sample container 2.
- the upper opening of the sample container 2 is closed with a septum 6 to seal the inside of the sample container 2, and the cap 5 is tightened to fix the septum 6.
- heating is performed at a constant temperature for a certain time.
- volatile gas is generated from the sample 4 as the sample gas and accumulates in the head space 3 in the sample container 2.
- the pressure in the head space 3 is increased to a predetermined pressure higher than atmospheric pressure. Therefore, a needle provided at the tip of the sample gas channel 8 is passed through the sample container 2 through the septum 6 of the sample container 2.
- the hexagonal valve 10 is in the state shown in FIG. 4, the on-off valve 24 is closed, and the on-off valve 14 is opened.
- a carrier gas having a constant pressure is supplied as a pressurized gas from the pressurized flow path 12, and the pressurized gas is supplied from the sample gas flow path 8 to the sample container 2 via the sample loop 16, so that the head space 3 has a predetermined pressure. It becomes.
- the pressure in the head space 3 at this time is a pressure adjusted by the automatic pressure control device 42. The pressure is detected by the pressure sensor 22.
- the on-off valve 14 is closed and the on-off valve 24 is opened with the hexagonal valve 10 as it is.
- the sample gas in the head space 3 is discharged from the sample gas flow path 8 through the sample loop 16 through the discharge flow path 20 and from the vent outlet 26 through the first resistance tube 28 to the atmosphere.
- a back pressure having a constant pressure higher than the atmospheric pressure is applied to the discharge channel 20 by the pressure channel 29.
- the magnitude of the back pressure is a pressure obtained by dividing the constant pressure adjusted by the automatic pressure control device 42 by the resistance tubes 28 and 30, and the initial pressure in the sample container 2 is adjusted by the automatic pressure control device 42.
- the back pressure of the discharge channel 20 is smaller than the initial pressure in the sample container 2. Therefore, the pressure in the sample loop 16 decreases toward the back pressure of the discharge channel 20 as shown by the solid line graph A in FIG. 7, and eventually becomes constant at the back pressure. The pressure in the sample loop 16 at this time is detected by the pressure sensor 22. If the resistance tube 28 is not provided and the vent outlet 26 is open to the atmosphere, the pressure in the sample loop 16 is directed toward atmospheric pressure as shown by the broken line graph B in FIG. It decreases and eventually becomes constant at atmospheric pressure.
- the sample gas contacts the pressure sensor 22.
- the test gas whose pressure is to be detected comes into contact with the pressure sensor, but unlike the flow sensor, it does not pass through the sensor. Therefore, there is little possibility that contamination by the test gas will lead to performance deterioration. Absent. If a flow rate sensor is provided somewhere in the discharge flow path, the flow rate sensor is contaminated with the test gas and its performance deteriorates.
- the sample is introduced into the gas chromatograph by switching the hexagonal valve 10 to the state shown in FIG.
- the carrier gas supplied from the carrier gas channel 34 passes through the sample loop 16, and the sample gas collected in the sample loop 16 is pushed out by the carrier gas and sent out from the analysis channel 36 to the gas chromatograph.
- the remaining gas divided by the split flow path 48 is sent to the separation column 46 and separated into sample components by the separation column 46.
- a detector 50 is provided downstream of the separation column 46, and sample components separated by the separation column 46 are detected by the detector 50.
- the sample introduction process to the gas chromatograph will be further described.
- Switching of the hexagonal valve 10 for sample introduction is performed in a time region a in which the pressure A in the sample loop 16 is stable, as shown by a solid line graph in FIG.
- the hexagonal valve 10 is switched to introduce the sample gas in the sample loop 16 into the gas chromatograph.
- the pressure in the sample loop 16 is monitored by the pressure sensor 22, and the hexagonal valve 10 is switched when the detected value of the pressure sensor 22 is stabilized.
- Switching of the hexagonal valve 10 can be automatically performed by a gas chromatograph control device in accordance with the detection output of the pressure sensor 22. It can also be switched manually by an operator.
- the concentration of the sample gas to be collected is constant even if there is a slight shift in time.
- the pressure at that time is higher than the atmospheric pressure, the sample gas concentration is higher than that in the case where the sample is collected in the atmospheric pressure state, and a highly sensitive analysis can be performed.
- the pressure channel 29 is not provided, as shown by the broken line graph B in FIG. 7, if the pressure is collected at a constant pressure, the atmospheric pressure is obtained. If the six-way valve 10 is to be switched at the same pressure, the six-way valve 10 must be switched at the timing indicated by b. Since the timing b is a timing at which the pressure in the sampling loop 16 is decreasing, if the timing for switching the six-way valve 10 is shifted, the concentration of the sample gas to be collected will fluctuate, and the reproducibility of the measurement results will be improved. descend.
- FIG. 8 shows an example of a gas chromatograph using the sample introduction apparatus of FIG.
- the gas chromatograph body 40 is the same as that shown in the embodiment of FIG.
- the pressure inlet 32a of the pressurization flow path 12 is connected to an automatic pressure control device 42 that supplies the carrier gas at a constant pressure so that the carrier gas used in the gas chromatograph is used as the pressure source of the pressurization flow path 12.
- the pressure introduction port 32b of the pressurizing channel 29 for applying the back pressure of the discharge channel 20 is connected to an automatic pressure control device 42a different from the automatic pressure control device 42.
- the automatic pressure control device 42a can supply an arbitrary gas as a pressurized gas.
- the automatic pressure control device 42a preferably uses a gas such as air or nitrogen that is less expensive than a gas used as a carrier gas in a gas chromatograph.
- the other configuration is the same as that of the embodiment of FIG.
- the operation is also the same as that of the embodiment of FIG.
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Abstract
Description
3 ヘッドスペース
8 試料ガス流路
10 六方バルブ
12 第1加圧流路
14,24 開閉弁
16 サンプルループ
20 排出流路
28,30 抵抗管
29 第2加圧流路
34 キャリアガス流路
36 分析流路
40 ガスクロマトグラフ本体
46 分離カラム
50 検出器
Claims (7)
- 試料から発生した試料ガスを溜めるヘッドスペースをもつ試料容器の前記ヘッドスペースにつながる試料ガス流路と、
大気圧よりも大きい一定の第1圧力の加圧ガス供給源に接続される第1加圧流路と、
前記試料ガスを採取するサンプルループと、
前記試料ガスを排出する排出流路と、
キャリアガスが供給されるキャリアガス流路と、
分析装置に接続される分析流路と、
前記第1加圧流路を前記ヘッドスペースに接続するヘッドスペース加圧流路構成、前記サンプルループを前記試料ガス流路と前記排出流路の間に接続する試料ガス採取用流路構成、及び前記サンプルループを前記キャリアガス流路と前記分析流路との間に接続する試料ガス導入流路構成の間で切り換える流路切換え機構と、
前記排出流路の下流に一端が接続され他端が大気に開放された第1抵抗管、及び前記排出流路の下流に一端が接続され他端が大気圧よりも大きい一定の第2圧力の加圧ガス供給源に接続される第2抵抗管を備えて、前記排出流路に前記第1、第2の抵抗管により前記第2圧力が分圧された大気圧より大きい一定圧力を印加する第2加圧流路と、
を備えたヘッドスペース試料導入装置。 - 前記第1加圧流路が接続される加圧ガス供給源と前記第2加圧流路が接続される加圧ガス供給源は共通の加圧ガス供給源である請求項1に記載のヘッドスペース試料導入装置。
- 前記第1加圧流路が接続される加圧ガス供給源と前記第2加圧流路が接続される加圧ガス供給源は異なる加圧ガス供給源である請求項1に記載のヘッドスペース試料導入装置。
- 試料ガスがキャリアガスとともに供給される分離カラム及び前記分離カラムにより分離された試料成分を検出する検出器を備えたガスクロマトグラフ本体と、
請求項1に記載のヘッドスペース試料導入装置と、を備え、
前記分析流路は分析装置としての前記ガスクロマトグラフ本体の前記分離カラムに接続されているガスクロマトグラフ。 - 前記第1加圧流路が接続される加圧ガス供給源は前記キャリアガス流路から供給されるキャリアガスと同じガスを加圧ガスとして供給するように構成されたものである請求項3に記載のガスクロマトグラフ。
- 前記第1加圧流路が接続される加圧ガス供給源と前記第2加圧流路が接続される加圧ガス供給源は共通の加圧ガス供給源である請求項5に記載のガスクロマトグラフ。
- 前記第1加圧流路が接続される加圧ガス供給源と前記第2加圧流路が接続される加圧ガス供給源は異なる加圧ガス供給源である請求項5に記載のガスクロマトグラフ。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2012/072635 WO2014038019A1 (ja) | 2012-09-05 | 2012-09-05 | ヘッドスペース試料導入装置とそれを備えたガスクロマトグラフ |
CN201280075395.0A CN104583770B (zh) | 2012-09-05 | 2012-09-05 | 顶空试料导入装置与具备该顶空试料导入装置的气相色谱仪 |
JP2014534086A JP5930049B2 (ja) | 2012-09-05 | 2012-09-05 | ヘッドスペース試料導入装置とそれを備えたガスクロマトグラフ |
US14/422,928 US9915634B2 (en) | 2012-09-05 | 2012-09-05 | Head space sample introduction device and gas chromatograph including same |
EP12884084.0A EP2876438B1 (en) | 2012-09-05 | 2012-09-05 | Head space sample introduction device and gas chromatograph including same |
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PCT/JP2012/072635 WO2014038019A1 (ja) | 2012-09-05 | 2012-09-05 | ヘッドスペース試料導入装置とそれを備えたガスクロマトグラフ |
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US (1) | US9915634B2 (ja) |
EP (1) | EP2876438B1 (ja) |
JP (1) | JP5930049B2 (ja) |
CN (1) | CN104583770B (ja) |
WO (1) | WO2014038019A1 (ja) |
Cited By (3)
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WO2020202868A1 (ja) * | 2019-04-01 | 2020-10-08 | 株式会社島津製作所 | ガス分析装置およびガスサンプリング装置 |
JP2022085314A (ja) * | 2020-11-27 | 2022-06-08 | 株式会社島津製作所 | 気体試料導入装置、および、気体試料導入装置のリークチェック方法 |
CN116773303A (zh) * | 2023-08-21 | 2023-09-19 | 成都市产品质量监督检验研究院 | 一种用于顶空检测中纤维类样品的前处理装置 |
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EP3428636A4 (en) * | 2016-03-07 | 2019-10-30 | Shimadzu Corporation | SAMPLE INTRODUCTION DEVICE FOR GAS CHROMATOGRAPHS |
CN105675776A (zh) * | 2016-04-07 | 2016-06-15 | 中科合成油技术有限公司 | 一种在线色谱稳定进样装置及方法 |
KR102020706B1 (ko) | 2017-01-20 | 2019-09-11 | 주식회사 엘지화학 | 이차전지 분리막 내 수분함량 측정방법 |
IT201700034608A1 (it) | 2017-03-29 | 2018-09-29 | Thermo Fisher Scient Spa | Metodo di campionamento per l’analisi gascromatografica dello spazio di testa |
WO2021111593A1 (ja) * | 2019-12-05 | 2021-06-10 | 株式会社島津製作所 | 試料導入装置 |
JP7447774B2 (ja) * | 2020-11-30 | 2024-03-12 | 株式会社島津製作所 | ガス分析装置およびガス分析装置の状態検出方法 |
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WO2020202868A1 (ja) * | 2019-04-01 | 2020-10-08 | 株式会社島津製作所 | ガス分析装置およびガスサンプリング装置 |
JP2022085314A (ja) * | 2020-11-27 | 2022-06-08 | 株式会社島津製作所 | 気体試料導入装置、および、気体試料導入装置のリークチェック方法 |
JP7392640B2 (ja) | 2020-11-27 | 2023-12-06 | 株式会社島津製作所 | 気体試料導入装置、および、気体試料導入装置のリークチェック方法 |
CN116773303A (zh) * | 2023-08-21 | 2023-09-19 | 成都市产品质量监督检验研究院 | 一种用于顶空检测中纤维类样品的前处理装置 |
CN116773303B (zh) * | 2023-08-21 | 2023-10-24 | 成都市产品质量监督检验研究院 | 一种用于顶空检测中纤维类样品的前处理装置 |
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US9915634B2 (en) | 2018-03-13 |
EP2876438A4 (en) | 2016-03-23 |
JPWO2014038019A1 (ja) | 2016-08-08 |
US20150233874A1 (en) | 2015-08-20 |
JP5930049B2 (ja) | 2016-06-08 |
EP2876438B1 (en) | 2018-05-23 |
EP2876438A1 (en) | 2015-05-27 |
CN104583770B (zh) | 2017-06-23 |
CN104583770A (zh) | 2015-04-29 |
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