JP2011242175A - Gas chromatograph mass spectrometer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas chromatograph mass spectrometer in which a septum or a glass insert of a sample vaporization chamber can be easily and properly replaced by anyone.SOLUTION: A gas chromatograph mass spectrometer 1 includes: an oven 20 for gas chromatography; a mass spectrometry unit 50; a sample vaporization chamber 30; a gas supply unit 40; and a control unit 60. When replacement work of a septum 32a or a glass insert 37a is started, the control unit 60 controls the gas supply unit 40 so that a flow rate of a carrier gas is brought into constant pressure, and then controls heaters 24, 38, and 72 so that a temperature is equal to or less than a replacement temperature at which the septum 32a or the glass insert 37a can be replaced. When the temperature becomes equal to or less than the replacement temperature to finish the replacement work of the septum 32a or the glass insert 37a, the control unit 60 controls the heaters 24, 38, and 72 so that the temperature is a spectrometry temperature, and controls the gas supply unit 40 so that a control method of the flow rate of the carrier gas is the same as that before the replacement work.

Description

  The present invention relates to a gas chromatograph mass spectrometer equipped with a sample vaporizing chamber having a septum and a glass insert.

In recent years, a gas chromatograph mass spectrometer combining a gas chromatograph unit (hereinafter referred to as “GC unit”), a mass spectrometer unit (hereinafter referred to as “MS unit”), and a control unit that controls the GC unit and the MS unit. An apparatus (hereinafter referred to as “GC / MS”) is widely used for qualitative analysis and quantitative analysis of various samples.
FIG. 5 is a schematic configuration diagram showing an example of a conventional GC / MS. The GC / MS 101 includes a GC unit 10, an MS unit 50, an interface unit 70 disposed between the GC unit 10 and the MS unit 50, and a control unit 160.

The control unit 160 is embodied by a personal computer, includes a CPU 161 and a memory 162, and further includes an input device 63 having a keyboard, a mouse, and the like, and a display device 64 that displays setting contents and analysis results. ing. By such a control unit 160, the operations of the GC unit 10, the MS unit 50, and the interface unit 70 are comprehensively controlled based on the setting content input by the input device 63.
The functions processed by the CPU 161 will be described in block form. A temperature control unit 161a that controls the first heater 24, the second heater 38 (see FIG. 2), the third heater 72, and the like, and a flow rate control unit (gas supply unit) 40. A flow rate control unit 161b that controls the flow rate, and an analysis control unit 61c that receives an ion intensity signal from the detector 55.

The GC unit 10 includes a gas chromatograph oven 20, a sample vaporization chamber 30 into which a sample is introduced, and a flow rate control unit (gas supply unit) 40 that supplies a carrier gas.
The gas chromatograph oven 20 includes a cubic housing 21 surrounded by four upper, lower, left, and right walls, a rear wall, and a front door serving as a front wall. Inside the housing 21, a circle through which a sample gas passes is provided. A tubular column 22, a first heater 24 for heating the housing 21, and a temperature sensor 25 for detecting the temperature T are accommodated.

In such a gas chromatograph oven 20, when an analysis is performed, an operator inputs an analysis temperature T ₁ ′ (for example, 200 ° C.) using the input device 63, so that the temperature controller 161 a of the CPU 161 can perform analysis. By storing the temperature T ₁ ′ in the memory 162 and supplying power to the first heater 24 based on the analysis temperature T ₁ ′ stored in the memory 162 and the temperature T detected by the temperature sensor 25. The inside of the housing 21 is set to the analysis temperature T ₁ ′.
Therefore, according to the gas chromatograph oven 20, when the sample gas is introduced into the inlet end of the column 22, each component in the sample gas is separated while passing through the inside of the column 22 at the analysis temperature T ₁ ′. After that, the separated components sequentially reach the outlet end of the column 22.

The interface unit 70 includes a cylindrical casing 71 and a third heater 72 that heats the casing 71. The outlet end of the column 22 is inserted into the casing 71 and extended to the ionization chamber 52 of the MS unit 50.
According to such an interface unit 70, the temperature at the outlet end of the column 22 can be maintained at the same level as the analysis temperature T ₁ ′ inside the gas chromatograph oven 20, and as a result, the flow of the sample gas Can be prevented from staying in the interface unit 70.

The MS unit 50 includes a rectangular parallelepiped vacuum chamber 51, a vacuum pump 56 for evacuating the inside of the vacuum chamber 51, and PFTBA (Perfluorotributylamine) for determining whether or not oxygen is present inside the column 22. And the like, and an ionization chamber 52, an ion lens 53, a quadrupole mass filter 54 as a mass separator, and an ion intensity signal are acquired inside the vacuum chamber 51. with a detector 55 is disposed in this order along the traveling direction of the ion, the pressure inside the ion gauge (ionization gauge) for detecting the (degree of vacuum) P _MS 57 of the vacuum chamber 51 is provided .

  According to such an MS unit 50, sample molecules are ionized in the ionization chamber 52, and the generated ions are extracted to the outside of the ionization chamber 52. The extracted ions are converged by the ion lens 53 and introduced into the quadrupole mass filter 54. A voltage obtained by superimposing a DC voltage and a high-frequency voltage is applied to the quadrupole mass filter 54 by a power supply circuit (not shown), and only ions having a mass (specifically, mass-to-charge ratio) corresponding to the applied voltage are applied. It passes through the space in the long axis direction of the quadrupole mass filter 54 and reaches the detector 55. At this time, for example, when the voltage applied to the quadrupole mass filter 54 is gradually changed, the mass of ions that can pass through the quadrupole mass filter 54 changes, so that the analysis control unit 61c performs the quadrupole mass filter. The mass spectrum indicating the relationship between the mass and the ion intensity is acquired by detecting the magnitude of the current in accordance with the number of ions reaching the detector 55 while gradually changing the voltage applied to 54. .

Next, the sample vaporization chamber 30 and the flow rate control unit 40 of the GC unit 10 will be described (see, for example, Patent Document 1). FIG. 2 is an enlarged cross-sectional view of the sample vaporizing chamber 30 and the flow rate control unit 40.
The sample vaporization chamber 30 includes a cylindrical metal case 31 and a second heater 38 that heats the outer peripheral surface of the case 31.
The casing 31 can be divided into an upper casing 31b and a lower casing 31a. By dividing the casing 31, a cylindrical glass insert 37a can be arranged inside. .

The upper housing 31b has a sample introduction port 32 that is formed on the upper surface and into which the liquid sample S is introduced.
The lower housing 31a is formed on the left side wall and is provided with a carrier gas introduction port 33 through which a carrier gas is introduced, a purge port 34 is formed on the right side wall through which the carrier gas is discharged, and is formed on the lower surface at the inlet end of the column 22. The column connection port 35 is connected, and the split port 36 is formed on the right side wall and discharges a part of the sample gas injected into the housing 31 together with the carrier gas.

  A substantially cylindrical silicon rubber septum 32a is disposed in the sample introduction port 32, and the septum 32a is fixed to the upper housing 31b by being pressed downward by a septum nut 32b. In such a septum 32a, when analyzing, the operator can drop the liquid sample S into the housing 31 by inserting the needle 91 of the microsyringe 90 containing the liquid sample S into the septum 32a. It is like that. Since the septum 32a has elasticity, the hole opened when the needle 91 is inserted is immediately closed when the needle 91 is removed.

  Inside the lower housing 31a, a glass insert 37a is disposed and supported by an annular seal ring 37b. In such a glass insert 37a, when an analysis is performed, the operator places the needle 91 of the microsyringe 90 on the upper portion of the internal space formed in the glass insert 37a, so that the liquid sample S can pass through the internal space of the glass insert 37a. It will vaporize while passing from the upper side to the lower side.

The upper housing 31b is fixed to the upper housing 31b by being pressed downward by a seal nut 37c.
The column connection port 35 is connected to the inlet end of the column 22 and is fixed by a column nut 35a.

  Carrier gas is sealed in the carrier gas supply source 41. The carrier gas supply source 41 is connected to one end of a gas introduction pipe 42, and the other end of the gas introduction pipe 42 is connected to a carrier gas introduction port 33 via a gas flow rate adjustment valve 43. The introduction pipe 42, the gas flow rate control valve 43, and the carrier gas supply source 41 constitute a flow rate control unit 40 for supplying carrier gas.

One end of a gas exhaust pipe 46 is connected to the split port 36, and a gas flow rate adjusting valve 47 is disposed in the gas exhaust pipe 46. Therefore, when the gas flow rate control valve 47 is open, a certain percentage of the carrier gas is discharged through the split port 36.
One end of a gas exhaust pipe 44 is connected to the purge port 34, and a pressure sensor 45 that detects the pressure P _GC inside the housing 31 is disposed in the gas exhaust pipe 44.

In such a sample vaporizing chamber 30 and the flow rate control unit 40, when an analysis is performed, an operator uses the input device 63 to input the flow rate of the carrier gas so that the flow rate of the carrier gas becomes “constant linear velocity”. The control unit 161b stores “constant linear velocity” in the memory 162, and controls the gas flow rate adjustment valve 43 so that the “linear velocity is constant” stored in the memory 162, whereby the carrier gas is supplied to the gas introduction pipe. In addition to being supplied to the upper portion of the casing 31 through 42 and controlling the gas flow rate adjustment valve 47, a predetermined amount of carrier gas flows into the column 22 and a predetermined amount of carrier gas flows to the split port 36. Shed.
At this time, when the casing 31 is heated above the vaporization temperature of the liquid sample S by the second heater 38 and the liquid sample S is injected into the internal space of the glass insert 37a, the liquid sample S is in the internal space of the glass insert 37a. It immediately vaporizes and rides on the carrier gas flow and is sent to the inlet end of the column 22 at a “linear velocity constant”.
“Constant linear velocity” means that the volume of the carrier gas passing through the cross-sectional area of the column 22 per unit time is controlled to be constant.

By the way, since the glass insert 37a disposed inside the housing 31 of the sample vaporizing chamber 30 is in direct contact with the sample S, the glass insert 37a is likely to become dirty due to adhesion of a vaporization residue or the like of the sample S. Therefore, when the glass insert 37a becomes dirty, it is necessary to replace the old glass insert 37a with the new glass insert 37a.
Here, an exchange operation for exchanging the glass insert 37a will be described. FIG. 3 is an exploded view of the sample vaporizing chamber 30.

First, if air enters the inside of the column 22 at a high analytical temperature T ₁ ′, the stationary phase film inside the column 22 is oxidized, and as a result, the lifetime of the column 22 is shortened. The operator inputs the replacement temperature T ₂ ′ (for example, 20 ° C.) using the input device 63 so as to lower the temperature T of the chamber 30 or the column 22 to near room temperature.
At this time, if the temperature T of the column 22 is in the vicinity of the replacement temperature T ₂ ′ while the flow rate of the carrier gas is set to be “constant linear velocity”, the linear velocity may be reduced depending on the length and inner diameter of the column 22. Since the carrier gas cannot be controlled with the pressure required to maintain it constant, the flow controller 161b of the CPU 161 may generate an error signal. Therefore, the operator using the input device 63, temperature T ₂ for replacement _'before entering, or flow rate of the carrier gas entering the "constant pressure", or, replacement temperature T _2' in Enter the pressure that can be controlled.
Here, “constant pressure” means that the pressure P _GC detected by the pressure sensor 45 is controlled to be constant.

Next, the operator confirms that the temperature T of the sample vaporizing chamber 30 and the column 22 is close to the replacement temperature T ₂ ′ while watching the display device 64, and then loosens and removes the seal nut 37b from the lower housing 31a. The glass insert 37a is extracted from the inside of the lower housing 31a. Next, the operator inserts a new glass insert 31a into the lower housing 31a and fastens the seal nut 37b to the lower housing 31a.
Finally, the operator using the input device 63, enter the _'analytical temperatures T ₁ to raise _up' the temperature T of the sample vaporization chamber 30 and column 22 temperatures T ₁ for analysis, further the flow rate of the carrier gas " It is input so that the linear velocity is constant, or the pressure before changing to the replacement temperature T ₂ ′ is input.

Further, when the elastic force of the septum 32a deteriorates due to long-term use, or when the number of uses increases and the number of holes increases, the holes are not completely closed. Gas leaks to the outside. If the analysis is performed in such a gas leak state, the retention time, which is the time when the peak of the chromatogram occurs, will shift or the peak area will be reduced, which hinders accurate analysis. It is necessary to perform replacement work.
Such an exchange operation for exchanging the septum 32a is also performed by the operator in the same procedure as the exchange operation for exchanging the glass insert 37a.

JP-A-11-101788

However, in an exchange operation as described above, in the case of an unskilled operator, a step of loosening and removing the seal nut 37b from the lower housing 31a before the temperature T of the sample vaporizing chamber 30 or the column 22 falls to near room temperature. As a result, the operator may be burned or air may be mixed into the high-temperature column 22 to shorten the life of the column 22.
Further, before the temperature T of the sample vaporizing chamber 30 or the column 22 falls to near room temperature, the carrier gas flow rate is input so as to be “constant pressure” or an appropriate pressure that can be controlled when the temperature is lowered. However, the temperature T of the sample vaporizing chamber 30 and the column 22 drops to near room temperature without the operator's input, and as a result, the CPU 161 cannot control the pressure and generates an error signal. There was something to do.

Further, the operator introduces PFTBA into the MS unit 50 and confirms the amount of oxygen present in the column 22 before the temperature T of the sample vaporizing chamber 30 and the column 22 is set to the analysis temperature T ₁ ′. It is also necessary to remove the air that has entered the sample vaporizing chamber 30 or the column 22.
In other words, the exchange work for exchanging the septum 32a and the glass insert 37a in the sample vaporization chamber 30 requires various steps to be executed according to a predetermined procedure, which is very difficult for an unskilled operator. .
Accordingly, an object of the present invention is to provide a gas chromatograph mass spectrometer that allows anyone to easily and accurately replace a septum or glass insert in a sample vaporization chamber.

  The gas chromatograph mass spectrometer of the present invention made to solve the above-mentioned problems is a gas chromatograph oven comprising a housing, a column disposed inside the housing, and a first heater for heating the housing, A case having a sample introduction port into which a liquid sample is introduced, a carrier gas introduction port into which a carrier gas is introduced, and a column connection port connected to the inlet end of the column; and a second for heating the case A sample vaporization chamber having a heater, a mass spectrometer connected to an outlet end of the column and having a detector for detecting an ionic strength signal of the liquid sample; and a carrier gas introduced into a carrier gas inlet of the sample vaporization chamber A gas supply unit to supply, and a control unit having an input device for inputting setting contents including the temperature for analysis, and a liquid sample is placed in the sample introduction port A septum into which the needle of the contained syringe is inserted is arranged, and a glass insert for vaporizing a liquid sample is arranged inside the casing, and the control unit is input by the input device A gas chromatograph mass spectrometer that acquires an ion intensity signal from the detector while controlling a first heater, a second heater, and a gas supply unit based on setting contents, wherein the control unit is configured to include the septum or glass When the replacement operation of the insert is started, after controlling the gas supply unit so that the flow rate of the carrier gas becomes a constant pressure, the heater is controlled so as to be below the replaceable temperature, and below the replaceable temperature. When the replacement work of the septum or glass insert is completed, the heater is controlled to reach the analysis temperature, and the carrier gas before the replacement work is started. So as to control the gas supply unit so that the control method of the flow rate of.

Here, the “exchangeable temperature” is an arbitrary temperature determined in advance by a designer or the like, and is an upper limit temperature at which the stationary phase film inside the column is not oxidized even if oxygen is present inside the column. For example, 30 ° C. or the like.
According to the gas chromatograph mass spectrometer of the present invention, the control unit controls the gas supply unit so that the flow rate of the carrier gas becomes “constant pressure” when the replacement work of the septum or the glass insert is started. Then, the heater is controlled so as to be equal to or lower than the replaceable temperature. In other words, the operator inputs the carrier gas flow rate so that the pressure is “constant pressure”, or inputs an appropriate value so that the carrier gas pressure can be controlled even when the temperature T of the column 22 reaches the “exchangeable temperature”. There is no need to input the replacement temperature T ₂ ′.
After that, when the temperature is lower than the replaceable temperature and the replacement work of the septum or the glass insert is finished, the heater is controlled so as to reach the analysis temperature T ₁ ′, and the flow rate of the carrier gas before the replacement work is started. For example, the gas supply unit is controlled so that the flow rate of the carrier gas becomes “constant linear velocity”. If the gas supply unit is controlled so that the flow rate of the carrier gas becomes “constant pressure” before the replacement operation is started, the gas supply unit so that the flow rate of the carrier gas becomes “constant pressure”. Will be controlled. That is, the operator does not need to input the analysis temperature T ₁ ′, and does not need to return the carrier gas pressure and flow rate to the values before the start of the exchange operation.

  As described above, according to the gas chromatograph mass spectrometer of the present invention, anyone can easily and accurately replace the septum and glass insert in the sample vaporization chamber.

(Means and effects for solving other problems)
In the gas chromatograph mass spectrometer according to the present invention, the method for controlling the flow rate of the carrier gas before the replacement operation is started controls the gas supply unit so that the flow rate of the carrier gas is constant. You may make it be.
Further, in the gas chromatograph mass spectrometer of the present invention, the mass analyzer includes an ionization vacuum gauge for measuring a vacuum degree of the mass analyzer, and the control unit is based on a signal from the ionization vacuum gauge, Whether or not to generate an error signal is determined, and the control unit supplies the gas so that the flow rate of the carrier gas becomes zero when the replacement work of the septum or the glass insert is started. And controlling the ionization vacuum gauge to be turned off, and controlling the flow rate of the carrier gas before the replacement work is started when the replacement work of the septum or the glass insert is completed. The gas supply unit may be controlled so as to be a method, and the ionization vacuum gauge may be turned on.
When the septum or glass insert is replaced, air enters the vacuum chamber through the column, and the controller is notified of the deterioration of the degree of vacuum indicated by the ionization vacuum gauge. According to the gas chromatograph mass spectrometer of the present invention, By turning off the power supply of the vacuum system, it is possible to prevent the notification of deterioration of the vacuum degree indicated by the ionization vacuum gauge. As a result, it is possible to prevent the operation of the entire gas chromatograph mass spectrometer from being stopped by determining that the control unit is dangerous during the replacement operation.

Further, in the gas chromatograph mass spectrometer of the present invention, the control unit acquires an ion intensity signal from the detector when the replacement work of the septum or the glass insert is finished, and based on the ion intensity signal. Thus, the intensity of the mass spectrum of nitrogen may be calculated to determine whether or not to control the heater so that the temperature for analysis is reached.
According to the gas chromatograph mass spectrometer of the present invention, the air that has entered the sample vaporizing chamber or the column can be expelled before the temperature of the sample vaporizing chamber or the column reaches the analysis temperature T ₁ ′.

Then, in the gas chromatograph mass spectrometer of the present invention, the control unit determines that the replacement work of the septum or the glass insert is started based on the replacement work start signal input by the input device, and the input device It may be determined that the replacement work of the septum or the glass insert has been completed based on the replacement work end signal input in.
Furthermore, in the gas chromatograph mass spectrometer according to the present invention, the control unit controls the heater so that the temperature becomes lower than the replaceable temperature, and then displays an image indicating that the temperature is lower than the replaceable temperature on the display device. May be.

It is a schematic block diagram which shows an example of GC / MS which concerns on this invention. It is an expanded sectional view of a sample vaporizing chamber and a flow control unit. It is an exploded view of a sample vaporization chamber. It is a flowchart which shows the procedure of the exchange method. It is a schematic block diagram which shows an example of conventional GC / MS.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments described below, and it goes without saying that various aspects are included without departing from the spirit of the present invention.

FIG. 1 is a schematic configuration diagram showing an example of GC / MS according to the present invention. In addition, the same code | symbol is attached | subjected about the thing similar to the conventional GC / MS101 mentioned above.
The GC / MS 1 includes a GC unit 10, an MS unit 50, an interface unit 70 disposed between the GC unit 10 and the MS unit 50, and a control unit 60.

The control unit 60 is embodied by a personal computer, includes a CPU 61 and a memory 62, and further includes an input device 63 having a keyboard, a mouse, and the like, and a display device 64 that displays setting contents and analysis results. ing.
The function processed by the CPU 61 will be described as a block. A temperature control unit 61a that controls the first heater 24, the second heater 38 (see FIG. 2), the third heater 72, and the like, and a flow rate control unit (gas supply unit) 40. A flow control unit 61b that controls the flow rate, an analysis control unit 61c that receives an ion intensity signal from the detector 55, and a determination unit 61d that determines whether air is present in the column 22 or not.

Further, the memory 62 stores in advance a replaceable temperature T ₂ (for example, 30 ° C.) as an upper limit temperature at which the stationary phase film inside the column 22 is not oxidized even if oxygen is present inside the column 22. At the same time, a preset temperature T ₃ (for example, 20 ° C.) is stored in advance as a target temperature for setting the temperature of the column 22 to the exchangeable temperature T ₂ or less in the GC / MS 1.
Further, the memory 62, the threshold I _th for determining whether or not the interior of the column 22 the oxygen of a predetermined amount is present are stored in advance.

The flow rate control unit 61 b causes the memory 62 to store “linear velocity constant” by inputting the carrier gas flow rate to “constant linear velocity” using the input device 63, and stores it in the memory 62. By controlling the gas flow rate adjustment valve 43 so that the “linear velocity is constant”, the carrier gas is supplied to the upper portion of the casing 31 through the gas introduction pipe 42 and the gas flow rate adjustment valve 47 is By controlling, a predetermined amount of carrier gas is allowed to flow to the column 22 and a predetermined amount of carrier gas is allowed to flow to the split port 36.
Similarly, the flow rate control unit 61 b causes the memory 62 to store “constant pressure” by inputting the carrier gas flow rate to “constant pressure” using the input device 63. The gas flow rate adjustment valve 43 is controlled so that the detected pressure P _GC is constant. It may be controlled by either “constant linear velocity” or “constant pressure” before the replacement work is started.
In addition, the flow control unit 61b of the present invention stores “replacement work start” in the memory 62 when the operator inputs “replacement work start” using the input device 63, and the “replacement work start” stored in the memory 62 is stored. Based on the “operation start”, the gas flow rate control valves 43 and 47 are controlled so that the flow rate of the carrier gas becomes “constant pressure”.
Furthermore, the flow control unit 61b of the present invention stores “replacement work end” in the memory 62 when the operator inputs “replacement work end” using the input device 63, and stores the “replacement work end” in the memory 62. After the temperature control unit 61a is set to the analysis temperature T ′ based on the “work end”, the carrier gas flow rate control method before the replacement work is started, for example, the carrier gas flow rate is “linear velocity”. The gas flow control valves 43 and 47 are controlled so as to be “constant”.

Temperature control unit 61a _'by entering the, temperatures T ₁ for _analysis' operator temperatures T ₁ for analysis by using the input device 64 is stored in the memory 64, the temperature for analysis stored in the memory 64 T ₁ Based on 'and the temperature T detected by a sensor such as the temperature sensor 25, the first heater 24, the second heater 38, and the third heater 72 are heated by supplying power to the analysis. Control to make the working temperature T ₁ '.
In addition, the temperature control unit 61 a of the present invention stores “replacement work start” in the memory 62 when the operator inputs “replacement work start” using the input device 64, and stores “replacement work start” in the memory 62. Based on the “work start”, the flow rate controller 61b supplies the electric power to the first heater 24, the second heater 38, and the third heater 72 after the carrier gas flow rate is set to “constant pressure”. by stopping the, so as to set the temperature T _3. Then, when the temperature T detected by the temperature sensor 25 is below exchangeable temperature T ₂ is indicated as "interchangeable work" on the display device 64.
Furthermore, the temperature control unit 61a of the present invention stores “replacement work end” in the memory 62 when the operator inputs “replacement work end” using the input device 64, and the “replacement work end” stored in the memory 62 is stored. By supplying power to the first heater 24, the second heater 38, and the third heater 72 based on the “work end” and the signal from the determination unit 61d, the analysis temperature T ₁ ′ is obtained. ing.

The analysis control unit 61c accumulates the ion intensity signal acquired by the detector 55 in the memory 62, executes various arithmetic processes based on the ion intensity signal, and performs control to display the analysis result on the display device 64. .
For example, a mass spectrum is created by taking the intensity of ions when mass scanning is performed for a certain holding time on the vertical axis and the mass-to-charge ratio (m / z) on the horizontal axis. At this time, a mass scan corresponding to each component that sequentially flows out from the column 22 is acquired by performing repeated mass scans intermittently at regular intervals.
Therefore, after acquiring such a large number of mass spectra, focusing on a certain m / z and developing the ion intensity in the time axis direction, the ion mass chromatogram of the selected mass-to-charge ratio can be obtained. Etc. can be obtained.

When the replacement of the septum 32a and the glass insert 37a is completed, the determination unit 61d introduces PFTBA into the MS unit 50, thereby obtaining an ion intensity signal from the detector 55, and based on the ion intensity signal. Whether the intensity ratio of the mass spectrum of nitrogen with respect to the intensity of the mass spectrum of PFTBA is calculated, and the first heater 24, the second heater 38, and the third heater 72 are controlled so as to become the analysis temperature T ₁ ′. Control to determine whether or not.
Specifically, the intensity ratio of the peak of the nitrogen ion (mass 28) to the intensity of the peak of the PFTBA ion (mass 69) is calculated based on the mass spectrum acquired by the analysis control unit 61c. When it is equal to or greater than the threshold value I _th , it is determined that a predetermined amount of oxygen is present in the column 22, that is, the first heater 24, the second heater 38, and the third heater 72 are set to the set temperature T _3. Remain in control. On the other hand, when the intensity ratio is less than the threshold value I _th, it is determined that a predetermined amount of oxygen does not exist in the column 22, that is, the first heater 24 and the second heater are set to the analysis temperature T ₁ ′. A signal is output to the temperature control unit 61a so as to control the control unit 38 and the third heater 72.

Next, a replacement method for replacing the glass insert 37a will be described. FIG. 4 is a flowchart showing the procedure of the exchange method.
First, in the process of step S101, the flow control unit 61b determines whether or not “start of replacement work” is input by the operator. When it is determined that “exchange work start” is not input, the process of step S101 is repeated.
On the other hand, when it is determined that “replacement work start” has been input, in the process of step S102, the flow rate control unit 61b controls the gas flow rate control valves 43 and 47 so that the flow rate of the carrier gas becomes “constant pressure”. To do.

Next, in the process of step S103, the temperature control unit 61a, by stopping to supply electric power to the first heater 24 and second heater 38 and the third heater 72, to set the temperature T _3.
Next, in the process of step S104, the temperature control unit 61a determines whether it is below exchangeable temperature _{T 2.} When determined not become exchangeable temperature T ₂ less repeats the processing in step S104.
On the other hand, when it is determined that it is below exchangeable temperature T ₂ is in the process of step S105, displays a "replaceable working" on the display device 64. Thereby, the operator recognizes that the glass insert 37a may be replaced.

Next, in the process of step S106, the operator replaces the glass insert 37a.
Next, in the process of step S107, the determination unit 61d determines whether or not “end of replacement work” has been input. When it is determined that “replacement work end” has not been input, the process of step S107 is repeated.
On the other hand, when it is determined that “end of replacement work” has been input, in the process of step S108, the determination unit 61d acquires the ion intensity signal from the detector 55 by introducing PFTBA into the MS unit 50, and the ion Based on the intensity signal, the intensity ratio of the peak of the nitrogen ion (mass 28) to the intensity of the peak of the PFTBA ion (mass 69) is calculated.

Next, in the process in step S109, the determination unit 61d determines whether the threshold value _{I th} or intensity ratio. When the intensity ratio is determined to be the threshold value I _th or repeats the processing in step S109.
On the other hand, when the intensity ratio is determined to be less than the threshold value I _th is in the process of step S110, the temperature control unit 61a, by supplying electric power to the first heater 24 and second heater 38 and the third heater 72 The analysis temperature is set to T ₁ ′.
Next, in the processing of step S111, the flow rate control unit 61b adjusts the gas flow rate so that the flow rate of the carrier gas before the replacement operation is started, for example, the flow rate of the carrier gas becomes “constant linear velocity”. The valves 43 and 47 are controlled.

  As described above, according to the gas chromatograph mass spectrometer 1 of the present invention, anyone can easily and accurately replace the septum 32a and the glass insert 37a of the sample vaporization chamber 30.

(Other embodiments)
(1) In the gas chromatograph mass spectrometer 1 described above, the flow rate controller 61b allows the flow rate of the carrier gas to be “constant pressure” when the operator inputs “start replacement” using the input device 63. In addition, the gas flow rate control valves 43 and 47 are configured to be controlled. However, when the operator inputs “start replacement operation” using an input device, the control unit performs gas control so that the flow rate of the carrier gas becomes zero. It is good also as a structure which controls so that the power supply of an ion gauge may be turned off while controlling a flow regulating valve. When the operator inputs “end of replacement work” using the input device, the control unit controls the flow rate of the carrier gas before the replacement work is started, for example, the flow rate of the carrier gas is “constant linear velocity”. The gas flow rate control valve is controlled so that the power of the ion gauge is turned on.
(2) In the gas chromatograph mass spectrometer 1 described above, the operator inputs “start replacement” using the input device 63, but the measuring instrument 45 changes the pressure P _GC inside the casing 31. By detecting this, a configuration may be adopted in which “start of replacement work” is set.

  The present invention can be used in a gas chromatograph mass spectrometer.

20: Gas chromatograph oven 21: Housing 22: Columns 24, 38, 72: Heater 31: Housing 32: Sample inlet 32a: Septum 33: Carrier gas inlet 35: Column connection port 37a: Glass insert 40: Flow rate control Unit (gas supply unit)
50: Mass spectrometry part (MS part)
55: Detector 60: Control unit 63: Input device 90: Syringe 91: Needle

Claims (6)

A gas chromatograph oven comprising a housing, a column disposed inside the housing, and a first heater for heating the housing;
A case having a sample introduction port into which a liquid sample is introduced, a carrier gas introduction port into which a carrier gas is introduced, and a column connection port connected to the inlet end of the column; and a second for heating the case A sample vaporization chamber comprising a heater;
A mass spectrometer having a detector connected to the outlet end of the column and detecting an ionic strength signal of the liquid sample;
A gas supply section for supplying a carrier gas to a carrier gas inlet of the sample vaporization chamber;
A control unit having an input device for inputting setting contents including the temperature for analysis,
A septum into which a syringe needle containing a liquid sample is inserted is arranged at the sample introduction port, and a glass insert for vaporizing the liquid sample is arranged inside the housing.
The control unit is a gas chromatograph mass spectrometer that acquires an ion intensity signal from the detector while controlling the first heater, the second heater, and the gas supply unit based on the setting content input by the input device. There,
The control unit controls the gas supply unit so that the flow rate of the carrier gas is constant when the replacement of the septum or the glass insert is started, and then controls the heater so that the temperature becomes a replaceable temperature or less. Control
A control method for controlling the flow rate of the carrier gas before the replacement work is started by controlling the heater so that the temperature becomes the analysis temperature when the replacement work of the septum or the glass insert is finished when the temperature becomes lower than the replaceable temperature. A gas chromatograph mass spectrometer characterized by controlling a gas supply unit. The method for controlling the flow rate of the carrier gas before the replacement operation is started is to control the gas supply unit so that the flow rate of the carrier gas is constant in linear velocity. Gas chromatograph mass spectrometer. The mass spectrometer includes an ionization vacuum gauge that measures the degree of vacuum of the mass analyzer,
The controller is configured to determine whether to generate an error signal based on a signal from the ionization gauge.
The control unit controls the gas supply unit so that the flow rate of the carrier gas becomes zero when the replacement work of the septum or the glass insert is started, and the power of the ionization vacuum gauge is turned off. Control to
When the replacement operation of the septum or glass insert is completed, the gas supply unit is controlled so that the flow rate of the carrier gas before the replacement operation is started, and the ionization vacuum gauge is turned on. The gas chromatograph mass spectrometer according to claim 1 or 2, wherein control is performed so that The control unit obtains an ion intensity signal from the detector when the replacement work of the septum or the glass insert is finished, and calculates the intensity of the mass spectrum of nitrogen based on the ion intensity signal. The gas chromatograph mass spectrometer according to any one of claims 1 to 3, wherein it is determined whether or not a heater is controlled so as to reach the analysis temperature. The control unit determines that the replacement work of the septum or the glass insert is started based on the replacement work start signal input by the input device,
5. The gas chromatograph mass according to claim 1, wherein it is determined that the replacement work of the septum or the glass insert is completed based on a replacement work end signal input by the input device. Analysis equipment. The said control part displays the image which shows that it became below replaceable temperature on a display apparatus, after controlling a heater so that it may become below replaceable temperature, Any one of Claims 1-5 characterized by the above-mentioned. A gas chromatograph mass spectrometer according to claim 1.

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