WO2016181853A1 - Gas chromatograph, temperature controller for same, and gas chromatograph temperature control method - Google Patents

Gas chromatograph, temperature controller for same, and gas chromatograph temperature control method Download PDF

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Publication number
WO2016181853A1
WO2016181853A1 PCT/JP2016/063327 JP2016063327W WO2016181853A1 WO 2016181853 A1 WO2016181853 A1 WO 2016181853A1 JP 2016063327 W JP2016063327 W JP 2016063327W WO 2016181853 A1 WO2016181853 A1 WO 2016181853A1
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Prior art keywords
temperature
column
power supply
set temperature
separation column
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PCT/JP2016/063327
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French (fr)
Japanese (ja)
Inventor
順子 柳谷
翁長　一夫
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日本写真印刷株式会社
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Publication of WO2016181853A1 publication Critical patent/WO2016181853A1/en

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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
    • G01N30/50—Conditioning of the sorbent material or stationary liquid
    • G01N30/52—Physical parameters
    • G01N30/54—Temperature

Definitions

  • the present invention relates to a gas chromatograph, a temperature control device therefor, and a gas chromatograph temperature control method.
  • Patent Document 1 in the temperature adjustment of the thermostat of the gas chromatograph, the proportional gain and / or the integral gain are instructed to the temperature control circuit based on the air temperature and the target temperature in the thermostat, Techniques have been proposed to suppress temperature overshoot.
  • the temperature of the separation column reaches the column temperature at which the sample is separated in a short time, it is difficult to suppress overshoot.
  • the voltage of the power source that supplies power to the heater is selected from an allowable voltage range such as 100 V to 240 V, and further set to any voltage within this allowable voltage range.
  • the difference in temperature control parameters tends to cause a difference in the heat generation status of the heater, which makes it difficult to suppress overshoot.
  • a gas chromatograph includes a separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature, a column heater for heating the separation column, and a separation column.
  • a temperature adjusting device for adjusting the temperature to the column temperature.
  • the temperature control device includes a set temperature indicating unit for indicating the set temperature of the separation column, a temperature measuring unit for measuring the temperature of the separation column, a set temperature indicated by the set temperature indicating unit, and a temperature measured by the temperature measuring unit.
  • a temperature control unit that controls the power output from the external power source to the column heater in accordance with the temperature difference between them and controls the temperature of the separation column to a set temperature.
  • the set temperature instructing unit changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature change period until the column temperature is reached.
  • the set temperature indicating unit changes the set temperature so as to gradually approach the column temperature as time passes during the set temperature changing period until the column temperature is reached. Therefore, if such control is not performed, the set temperature becomes lower than the column temperature during a period in which overshoot occurs. Thus, overshoot can be suppressed by generating the difference between the set temperature and the column temperature in the period.
  • the column heater may be configured to be able to supply power from an external power supply having a power supply voltage selected from a predetermined allowable voltage range.
  • the temperature adjustment device may be configured to be able to control power output to the column heater from an external power supply having the power supply voltage.
  • the gas chromatograph described above may further include a power supply voltage detection unit that detects the power supply voltage of the external power supply.
  • the temperature control unit may be configured to change the pulse width setting according to the power supply voltage detected by the power supply voltage detection unit and perform PWM control on the power output from the external power supply to the column heater.
  • the separation column may have a cylindrical resin molded product and a metal coating covering the outer surface of the resin molded product.
  • the column heater may be arranged in close contact with the metal coating and configured to heat the metal coating.
  • the set temperature instructing unit may be set so that the rate of change of the temperature difference between the set temperature and the column temperature decreases with time.
  • a temperature control device for a gas chromatograph includes a separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature, and a column heater for heating the separation column. Used for gas chromatographs.
  • the temperature adjusting device is a device for adjusting the temperature of the separation column to the column temperature.
  • the temperature control device includes a set temperature indicating unit for indicating the set temperature of the separation column, a temperature measuring unit for measuring the temperature of the separation column, a set temperature indicated by the set temperature indicating unit, and a temperature measured by the temperature measuring unit.
  • a temperature control unit that controls the power output from the external power source to the column heater in accordance with the temperature difference between them and controls the temperature of the separation column to a set temperature.
  • the set temperature instruction unit changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature change period until the column temperature is reached.
  • the set temperature indicating unit is changed so that the set temperature gradually approaches the column temperature as time passes during the set temperature changing period until the column temperature is reached. To do. Therefore, if such control is not performed, the set temperature is lower than the column temperature during a period in which overshoot has occurred.
  • the column heater may be configured to be able to supply power from an external power supply having a power supply voltage selected from a predetermined allowable voltage range.
  • the temperature control unit includes a power supply voltage detection unit that detects the power supply voltage of the external power supply, and changes the pulse width setting according to the power supply voltage so as to PWM-control the power output from the external power supply to the column heater. It may be configured.
  • a gas chromatograph temperature control method includes a separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature, and a column heater for heating the separation column. Used for gas chromatographs.
  • the temperature adjustment method is a method of adjusting the temperature of the separation column to the column temperature.
  • the temperature adjustment method includes a set temperature indicating step for indicating the set temperature of the separation column, a temperature measuring step for measuring the temperature of the separation column, a set temperature indicated in the set temperature indicating step, and a temperature measured in the temperature measuring step.
  • the set temperature instruction step the set temperature is changed so as to gradually approach the column temperature as time elapses in the set temperature change period until the column temperature is reached.
  • the set temperature is changed so that the set temperature gradually approaches the column temperature as time elapses in the set temperature indication step until the column temperature is reached. To do. Therefore, if such control is not performed, the set temperature becomes lower than the column temperature during a period in which overshoot occurs. Thus, overshoot can be suppressed by generating the difference between the set temperature and the column temperature in the period.
  • the temperature of the separation column can be reached in a short time while suppressing overshoot.
  • the temperature of the separation column can be reached in a short time while suppressing overshoot even with an inexpensive gas chromatograph.
  • the conceptual diagram which shows an example of a structure of the gas chromatograph which concerns on embodiment of this invention.
  • the top view which shows an example of the separation column used with the gas chromatograph of FIG.
  • the top view which shows the state by which the column heater was wound around the separation column of FIG.
  • FIG. 4 is a schematic diagram showing a cross-sectional structure cut along a line II in FIG. 3.
  • the top view which shows the state by which the heat insulating material was wound around the separation column of FIG.
  • the conceptual diagram which shows an example of the gas sensor used with the gas chromatograph of FIG.
  • the block diagram for demonstrating the structure of the gas chromatograph of FIG. The block diagram for demonstrating an example of a structure of the temperature control apparatus used with the gas chromatograph of FIG.
  • a waveform diagram of a triangular wave generated inside the PWM control circuit (b) a waveform diagram showing an example of a PWM signal when the power supply voltage of the external power supply is high, and (c) a case where the power supply voltage of the external power supply is low Waveform diagram showing an example of a PWM signal, (d) Waveform diagram showing an example of a voltage waveform applied to the column heater when the power supply voltage of the external power supply is high, (e) Application to the column heater when the power supply voltage of the external power supply is low The wave form diagram which shows an example of the voltage waveform performed. The graph which shows the change of the temperature of a separation column when setting temperature is constant when the power supply voltage of an external power supply is high.
  • the graph which shows the change of the temperature of a separation column when setting temperature is constant when the power supply voltage of an external power supply is low.
  • the graph which shows the change of the temperature of a separation column when setting temperature is brought close to column temperature gradually when the power supply voltage of an external power supply is high.
  • the graph which shows the change of the temperature of a separation column when setting temperature is made to approach column temperature gradually when the power supply voltage of an external power supply is low.
  • the gas chromatograph 10 includes an air pump 11, a gas purification device 12, a flow rate regulator 13, a flow rate sensor 14, a separation column 15, a semiconductor gas sensor 16, and a column heater. 20 and a temperature control device 30. Many of the components constituting the temperature adjustment device 30 are mounted on the control board 50.
  • the separation column 15, the semiconductor gas sensor 16, and the column heater 20 are included in the sensor column block 60.
  • a control thermistor 33 which is one of the components constituting the temperature adjustment device 30, is included in the sensor column block 60.
  • the control thermistor 33 is, for example, an NTC thermistor.
  • the carrier gas of the gas chromatograph 10 is air.
  • the air pump 11 is a device for flowing air as a carrier gas to the gas chromatograph 10.
  • the gas purification device 12 is a device that purifies the carrier gas, and includes, for example, a gas adsorbent and a gas decomposition catalyst in order to purify the carrier gas.
  • the gas adsorbent is, for example, activated carbon or silica gel.
  • the gas decomposition catalyst is an oxidation catalyst.
  • the flow rate adjuster 13 adjusts the flow rate of the carrier gas sent to the separation column 15 to be a constant amount.
  • a linear valve having a characteristic that the flow rate is proportional to the valve opening within a predetermined range is used.
  • the flow sensor 14 measures the flow rate of the carrier gas sent to the separation column 15.
  • the separation column 15 is a cylindrical device that separates a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature.
  • a capillary column may be used as the separation column 15.
  • a sample introduction part 17 for introducing a sample is provided on the upstream side of the separation column 15.
  • the semiconductor gas sensor 16 is disposed on the downstream side of the separation column 15 and detects the component of the sample that has passed through the separation column 15.
  • the semiconductor gas sensor 16 is a semiconductor sensor as described later, for example.
  • the separation column 15 separates the sample at a predetermined column temperature.
  • a column heater 20 is attached to the separation column 15.
  • the column heater 20 is a rubber heater that is a planar heating element. The temperature of the column heater 20 is adjusted by the temperature adjustment device 30.
  • FIG. 2 shows the appearance of the separation column 15.
  • FIG. 3 shows a state in which the column heater 20 is wound around the separation column 15.
  • FIG. 4 is a schematic view of a cross section taken along the line II of FIG.
  • the separation column 15 has a cylindrical resin molded product 15a (FIG. 4) and a metal coating 15b that covers the outer surface of the resin molded product 15a.
  • the resin molded product 15a is made of, for example, a polyfluorinated ethylene resin, more specifically, for example, polytetrafluoroethylene.
  • the metal coating 15b is formed using, for example, a copper tube or a copper foil. As shown in FIG.
  • a cylindrical resin molded product 15a is filled with a filler 15c that forms a stationary phase.
  • the filler 15c is, for example, diatomaceous earth, molecular sieve, porous polymer, or alumina.
  • the filler 15c may be coated with a liquid phase.
  • a measurement thermistor 32 and a control thermistor 33 are attached to a central portion in the longitudinal direction of the separation column 15 by a binding band 31.
  • Thermal fuses 34 are attached to positions on both sides of the measurement thermistor 32 and the control thermistor 33.
  • a heat insulating material 35 is further wound on the separation column 15 around which the column heater 20 is wound.
  • the heat insulating material 35 is, for example, a foamed urethane sheet.
  • FIG. 6 is a conceptual diagram showing a semiconductor gas sensor 16 as an example of a gas sensor used in the gas chromatograph 10 of FIG.
  • a semiconductor gas sensor 16 includes a gas sensitive body 16a mainly composed of a metal oxide semiconductor, a coiled heater combined electrode 16b embedded in the gas sensitive body 16a, and the center of the coil of the heater combined electrode 16b.
  • a semiconductor resistance detection electrode 16c embedded in the gas sensitive body 16a so as to penetrate the vicinity thereof, and electrode pads 16d and 16e are provided. Both ends of the heater combined electrode 16b are connected to two electrode pads 16d.
  • the semiconductor resistance detection electrode 16c is connected to the electrode pad 16e.
  • the electrode pads 61d and 16e are used for taking out a change in load resistance between the heater electrode 16b and the semiconductor resistance detection electrode 16c.
  • the semiconductor gas sensor 16 detects a gas component to be detected based on a change in the resistance value of the gas sensitive body 16a.
  • gas components to be detected include volatile sulfides (VSC) that cause bad breath, and examples of VSCs include hydrogen sulfide, methyl mercaptan, ethyl mercaptan, and dimethyl sulfide.
  • VSC volatile sulfides
  • the metal oxide that forms the gas sensitive body 16a include SnO 2 , In 2 O 3 , ZnO, and WO 3 .
  • FIG. 7 is a block diagram of the gas chromatograph 10 for explaining the temperature control device 30 and the configuration around it. 7 shows the air pump 11, the gas purification device 12, the flow rate regulator 13, the flow rate sensor 14, the semiconductor gas sensor 16, the column heater 20, and the temperature adjustment device 30 shown in FIG. Also shown is a sensor column block 60 including a control substrate 50 and a separation column 15 (see FIG. 1). Connected to the control board 50 are various switches (not shown) and a switch / LED board 70 on which a power LED 71, an error LED 72, a ready LED 73, and a buzzer 74 for notifying the operation state of the gas chromatograph 10 are mounted. Has been.
  • the control board 50 is connected to a personal computer 80 for storing data transmitted to and received from the control board 50 and displaying the data on the display screen 81. Furthermore, an external power supply 100 is connected to the control board 50.
  • the external power supply 100 that can be connected to the control board 50 is a commercial AC power supply having a power supply voltage selected from an allowable voltage range of 90 V to 264 V, for example. In Japan, for example, a single-phase 100V or single-phase 200V AC power supply is connected.
  • the power LED 71 is lit when connected to the external power supply 100.
  • the ready LED 73 is lit when the gas chromatograph 10 becomes measurable.
  • the error LED 72 is lit when the gas chromatograph 10 malfunctions.
  • the control board 50 further includes an analog-digital conversion unit 51, a VH control unit 52, a linear valve control unit 53, and a DC voltage control unit 54.
  • the control board 50 includes a central processing unit (CPU) 38, a power supply voltage detection unit 36, a temperature control unit 37, and a zero-cross semiconductor relay (hereinafter referred to as ZCSSR) 39 as components constituting the temperature adjustment device 30. And have been implemented.
  • the analog / digital converter (A / D converter) 51 is connected to the electrode pads 16d and 16e.
  • the analog-to-digital conversion unit 51 performs the resistance of the gas sensitive body 16a.
  • the output voltage of the semiconductor gas sensor 16 that changes according to the value is converted into a digital signal and output to the CPU 38 of the temperature control device 30.
  • the VH controller 52 is connected to the two electrode pads 16d of the semiconductor gas sensor 16, and controls the temperature of the gas sensitive body 16a by controlling the voltage applied to the heater electrode 16b.
  • the temperature control device 30 is a device that adjusts the temperature of the separation column 15 to the column temperature.
  • the temperature adjustment device 30 includes a control thermistor 33, a power supply voltage detection unit 36, a temperature control unit 37, a CPU 38, a ZCSSR 39, and a resistor 44.
  • the temperature control unit 37 of the temperature adjustment device 30 includes a proportional-integral control circuit (hereinafter referred to as a PI control circuit) 41, a PWM control circuit 42, and a thermistor disconnection detection circuit 43.
  • the CPU 38 forms a set temperature instruction unit 38a by executing software.
  • the set temperature instruction unit 38 a instructs the set temperature of the separation column 15.
  • a control thermistor 33 and a CPU 38 are connected to the PI control circuit 41 of the temperature control unit 37.
  • the control thermistor 33 is a temperature measurement unit for measuring the temperature of the separation column 15.
  • the temperature control unit 37 controls the power output from the external power source 100 to the column heater 20 according to the temperature difference between the set temperature indicated by the set temperature indicating unit 38a and the temperature measured by the control thermistor 33, thereby separating the separation column.
  • 15 has a function of controlling the temperature of 15 to the set temperature.
  • the PI control circuit 41 compares the set temperature indicated by the set temperature indicating unit 38a of the CPU 38 with the temperature of the separation column 15 measured by the control thermistor 33, and compares the set temperature thus compared with the temperature of the separation column 15. An output voltage OV corresponding to the temperature difference is output.
  • a power supply voltage detection unit 36 is also connected to the PI control circuit 41.
  • the power supply voltage detector 36 determines whether the power supply voltage of the external power supply 100 is greater than or equal to the value near the center of the allowable voltage range or smaller than the value near the center, and outputs the determination result. For example, if the allowable voltage range is from 90V to 264V, for example, the value near the center of the allowable voltage range is a value selected from 130V to 200V.
  • the power supply voltage detection unit 36 outputs “Low” when the external power supply 100 is 100 V, and the power supply voltage detection unit 36 outputs “Low” when the external power supply 100 is 200 V. “High” is output.
  • the PI control circuit 41 has a fluctuation range of the output voltage OV2 when the power supply voltage detection unit 36 outputs “High” rather than a fluctuation range ROV1 of the output voltage OV1 when the power supply voltage detection unit 36 outputs “Low”.
  • ROV2 is set to be small (see FIG. 9A).
  • the PWM control circuit 42 outputs a pulse signal PS having a length corresponding to the output voltage OV of the PI control circuit 41 to the ZCSSR 39.
  • the column heater 20 and the external power supply 100 are connected in series between the two terminals of the ZCSSR 39 of the temperature control device 30.
  • the ZCSSR 39 When the ZCSSR 39 is turned on, power is supplied from the external power supply 100 by the column heater 20, and when the ZCCSR 39 is turned off, the supply of power from the external power supply 100 to the column heater 20 is stopped.
  • the ZCCSR 39 has a built-in zero cross circuit for triggering when the AC voltage of the external power supply 100 is near zero voltage.
  • the application of the voltage of the external power supply 100 to the column heater 20 is started at the first zero voltage after the pulse signal PS of the PWM control circuit 42 is output, and the column heater 20 is started at the first zero voltage after the output of the pulse signal PS is finished.
  • the application of the voltage of the external power supply 100 is stopped.
  • a voltage having the shape of a triangular wave TW is generated inside the PWM control circuit. If the period of the triangular wave TW is 120 ms, for example, the period of the PWM signal generated by the PWM control circuit 42 is 120 ms. When there is no temperature difference between the set temperature and the temperature of the separation column 15 or when the temperature of the separation column 15 is higher than the set temperature, the output voltage OV becomes 0V. The PWM control circuit 42 does not output a PWM signal when the output voltage OV of the PI control circuit 41 is 0V. As shown in FIGS.
  • the PWM signal P1 is output only during the period when the voltage of the triangular wave TW is below the upper limit value.
  • the maximum value (duty) of the PWM signal P1 when the power supply voltage of the external power supply 100 is 100 V is set to 80 ms.
  • the upper limit value of the fluctuation range ROV2 of the output voltage OV2 when the power supply voltage detection unit 36 outputs “High” is input.
  • the PWM signal P2 is output.
  • the maximum value (duty) of the PWM signal P1 when the power supply voltage of the external power supply 100 is 200 V is set to 20 ms.
  • the power supply voltage of the external power supply 100 is high (for example, 200 V)
  • the voltage applied to the column heater 20 is high, but supplied from the external power supply 100.
  • the time required for this is shortened.
  • the power supply voltage of the external power supply 100 is low (for example, 100 V)
  • the voltage applied to the column heater 20 is low, but supplied from the external power supply 100. The time will be longer.
  • the maximum power supplied to the column heater 20 is adjusted to a close value.
  • the waveform indicated by the solid line is the waveform of the voltage applied to the column heater 20.
  • FIG. 10 is a graph showing the measured temperature of the separation column 15 when the power supply voltage of the external power supply 100 is 264V
  • FIG. 11 shows the measured temperature of the separation column 15 when the power supply voltage of the external power supply 100 is 90V. It is a graph.
  • the atmospheric temperature when these measurements are performed is 10 ° C.
  • the gas chromatograph 10 is set so that the temperature of the separation column 15 is stabilized at the column temperature necessary for measurement in a short time within 30 minutes so as to be suitable for use in, for example, a medical field or a school laboratory. .
  • the temperature of the separation column 15 is set to be stable to the column temperature necessary for measurement within 30 minutes. ing. Therefore, when the power supply voltage is 264 V, that is, when the temperature is relatively easy to rise, the temperature of the separation column 15 greatly overshoots.
  • FIG. 12 and 13 show changes with time in the measurement temperature of the separation column 15 when the set temperature instruction unit 38a gradually brings the set temperature close to the column temperature, for example, 35 ° C.
  • FIG. 12 is a graph showing the measured temperature of the separation column 15 when the power supply voltage of the external power supply 100 is 264V
  • FIG. 13 shows the measured temperature of the separation column 15 when the power supply voltage of the external power supply 100 is 90V. It is a graph. 12 and 13, the thick line is the temperature, and the thin line is the control output from the set temperature instruction unit 38a.
  • the set temperature instruction unit 38a gradually brings the set temperature closer to the column temperature during the set temperature change period St.
  • the value of this hyperbolic function f becomes the set temperature.
  • ⁇ is a constant appropriately selected through experiments
  • x is a time (sec) variable.
  • the set temperature change period St is set from the beginning of the heating of the column heater 20.
  • the initial period Bt corresponds to 60% of the amount of heat necessary to reach the column temperature from the ambient temperature. You may make it give electric energy.
  • the power supply voltage of the external power supply 100 is applied without performing PWM control.
  • the external power supply 100 is directly connected to the column heater 20 for an initial period Bt of about 1 and a half minutes, and in the case of the 90V external power supply 100, the external power supply 100 is connected to the column heater for an initial period Bt of about 3 minutes. Directly connected to 20.
  • the set temperature instruction unit 38a matches the set temperature with the column temperature. After the set temperature instruction unit 38a matches the set temperature to the column temperature, the temperature control performed by the PI control circuit 41 is normal PI control.
  • the temperature of the separation column 15 is set to be stable to the column temperature necessary for measurement within 30 minutes.
  • the power supply voltage is 264 V, that is, when the temperature is relatively easy to rise, the temperature of the separation column 15 hardly overshoots as shown in FIG.
  • the set temperature instruction unit 38 a instructs the set temperature of the separation column 15.
  • a control thermistor 33 that is a temperature measuring unit measures the temperature of the separation column 15.
  • the temperature control unit 37 controls the power output from the external power source 100 to the column heater 20 according to the temperature difference between the set temperature indicated by the set temperature indicating unit 38a and the temperature measured by the control thermistor 33, thereby separating the separation column.
  • the temperature of 15 is controlled to the set temperature.
  • the set temperature instructing unit 38a changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature changing period until the column temperature is reached. As described in the above example, in the set temperature change period St until the set temperature instruction unit 38a reaches the column temperature (35 ° C.
  • the set temperature is gradually increased to the column temperature as time elapses. Change to get closer.
  • the set temperature is made constant without performing such control, overshoot occurs as it appears remarkably in FIG. 10 of the reference example.
  • the set temperature is changed so as to gradually approach the column temperature as time elapses, as shown in FIG. 12 of the embodiment, the set temperature is higher than the column temperature during the period when the overshoot has occurred. Also lower. Thus, overshoot can be suppressed by generating a difference between the set temperature and the column temperature during the period.
  • the column heater 20 is configured to be able to supply power from the external power supply 100 having a power supply voltage selected from an allowable voltage range of 90 V to 264 V.
  • the temperature control apparatus 30 is comprised so that control of the electric power output with respect to the column heater 20 from the external power supply 100 which has such a power supply voltage is possible.
  • the example at the time of selecting 100V and 200V from the allowable voltage range is demonstrated.
  • setting of the temperature control device 30 is difficult in the prior art. .
  • the set temperature instructing unit 38a changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature changing period St until the column temperature is reached. Therefore, overshoot can be easily suppressed while reducing the time to reach the column temperature over the entire allowable voltage range.
  • the temperature adjustment device 30 includes a power supply voltage detection unit 36 that detects the power supply voltage of the external power supply 100.
  • the temperature control unit 37 is configured to change the setting of the pulse width according to the power supply voltage detected by the power supply voltage detection unit 36 and to perform PWM control of the power output from the external power supply 100 to the column heater 20. Yes.
  • the power supply voltage detection unit 36 detects 100 V lower than 160 V
  • the maximum value (duty) of the period during which the PWM signal P1 is output becomes as long as 80 ms.
  • the power supply voltage detection unit 36 detects 200 V higher than 160 V, the maximum value of the period during which the PWM signal P2 is output becomes 20 ms.
  • the amount of power supplied to the column heater 20 can be made close, and temperature control that is difficult to overshoot can be easily performed.
  • the determination based on one threshold value 160 V in the above-described embodiment
  • the maximum value of the period during which the PWM signal is output may be changed continuously.
  • the separation column 15 has a cylindrical resin molded product 15a and a metal coating 15b covering the outer surface of the resin molded product 15a, and the column heater 20 is disposed in close contact with the metal coating 15b to heat the metal coating 15b. Is configured to do. Since the heat capacities of the resin molded product 15a and the metal coating 15b are small, the temperature of the separation column 15 can be quickly reached the column temperature. On the other hand, conventionally, in the separation column 15 constituted by using the resin molded product 15a and the metal coating 15b, overshoot at the time of temperature adjustment tends to occur. On the other hand, in the present embodiment, the set temperature instructing unit 38a changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature change period St until the column temperature is reached. Can be sufficiently suppressed.
  • the set temperature instruction unit 38a is set so that the change rate of the temperature difference between the set temperature and the column temperature decreases with time using a hyperbolic function f as shown in FIG. Since such setting is performed, the effect of suppressing the overshoot is higher than when the rate of change of the temperature difference between the set temperature and the column temperature is constant regardless of the passage of time.
  • the temperature adjustment device 30 is configured using the PI control circuit 41, but the temperature adjustment device 30 may have other configurations.
  • the temperature adjusting device 30 is configured by another control circuit that controls the power output from the external power source to the column heater in accordance with the temperature difference between the set temperature indicated by the set temperature indicating unit and the temperature measured by the temperature measuring unit. May be.
  • a proportional control circuit P control circuit
  • P control circuit that performs proportional control
  • the separation column 15 is configured to include the cylindrical resin molded product 15a and the metal coating 15b covering the outer surface thereof.
  • the configuration of the separation column 15 is not limited to this. It is not something that can be done.
  • a cylindrical glass molded product and / or a cylindrical metal molded product can be used instead of the cylindrical resin molded product 15a and the metal coating 15b covering its outer surface.
  • the control thermistor 33 is used for the temperature measurement unit.
  • the members constituting the temperature measurement unit are not limited to the thermistor, and for example, a thermocouple, a diode, a transistor, or an IC may be used. it can.
  • the control thermistor 33 which is a temperature measuring element used for measurement is not limited to one, and a plurality of thermistors can be used. For example, an average value or a median value can be used as the measurement value output from the temperature measurement unit when a plurality of temperature measurement units are used.
  • the set temperature instruction unit 38a is formed by the CPU 38 using software has been described.
  • the set temperature instruction unit 38a may be configured by, for example, hardware of an electronic circuit.
  • the function used for changing the set temperature so as to gradually approach the column temperature as time passes in the change period St is not limited to this.
  • a function obtained by expanding the above function into a polynomial of x may be used.
  • the set temperature may be changed so as to gradually approach the column temperature as time passes by using a polynomial of x that is not related to the above function.
  • the present invention can be widely applied to a gas chromatograph, its temperature control device, and a gas chromatograph temperature control method.

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Abstract

[Problem] To provide an inexpensive gas chromatograph capable of suppressing overshoot while causing a separation column temperature to quickly stabilize at a column temperature at which a sample is separated. [Solution] A setting temperature request unit 38a requests a separation column 15 setting temperature. A control thermistor 33 that serves as a temperature measurement unit measures the temperature of a separation column 15. A temperature control unit 37 controls the power output from an external power supply 100 to a column heater 20 according to the temperature difference between the setting temperature requested by the setting temperature request unit 38a and the temperature measured by the control thermistor 33 and controls the separation column 15 temperature such that the same becomes the setting temperature. During a setting temperature variation period until a column temperature is reached, the setting temperature request unit 38a changes the setting temperature such that the same gradually approaches the column temperature over time.

Description

ガスクロマトグラフ及びその温度調節装置並びにガスクロマトグラフの温度調節方法Gas chromatograph, temperature control device thereof, and temperature control method of gas chromatograph
　本発明は、ガスクロマトグラフ及びその温度調節装置並びにガスクロマトグラフの温度調節方法に関する。 The present invention relates to a gas chromatograph, a temperature control device therefor, and a gas chromatograph temperature control method.
　従来のガスクロマトグラフの温度調整では、例えば特許文献１（特開２０１４－２１１３８６号公報）に記載されているように、ヒータによる発熱量を操作量として比例制御（Ｐ制御）、比例積分制御（ＰＩ制御）、又は比例積分微分制御（ＰＩＤ制御）に基づき制御を行う温度制御回路がしばしば用いられる。しかし、比例制御（Ｐ制御）、比例積分制御（ＰＩ制御）、又は比例積分微分制御（ＰＩＤ制御）に基づきヒータによる発熱量を操作量として制御しても、温度がカラム温度に達した後にオーバーシュートする場合がある。 In conventional temperature adjustment of a gas chromatograph, for example, as described in Patent Document 1 (Japanese Patent Laid-Open No. 2014-212386), the amount of heat generated by a heater is used as a manipulated variable for proportional control (P control) and proportional integral control (PI). Control), or a temperature control circuit that performs control based on proportional-integral-derivative control (PID control) is often used. However, even if the amount of heat generated by the heater is controlled as the manipulated variable based on proportional control (P control), proportional integral control (PI control), or proportional integral derivative control (PID control), the temperature will exceed after reaching the column temperature. May shoot.
特開２０１４－２１１３８６号公報Japanese Patent Application Laid-Open No. 2014-212386
　そこで、特許文献１には、ガスクロマトグラフの恒温槽の温度調整において、恒温槽内の空気温度と目標温度とに基づき比例ゲイン及び／又は積分ゲインを温度制御回路に指示することで、恒温槽の温度のオーバーシュートを抑える技術が提案されている。
　しかし、短い時間で分離カラムの温度を試料の分離を行うカラム温度に到達させようとすると、オーバーシュートの抑制が難しくなる。特に、ヒータに電力を供給する電源の電圧を、例えば１００Ｖから２４０Ｖなどのように許容電圧範囲の中から選択して、さらにこの許容電圧範囲内のいずれかの電圧に設定すればよい場合には、温度制御のパラメータの違いが原因でヒータの発熱状況に差異が生じる傾向があり、そのためオーバーシュートの抑制が難しくなる。 Therefore, in Patent Document 1, in the temperature adjustment of the thermostat of the gas chromatograph, the proportional gain and / or the integral gain are instructed to the temperature control circuit based on the air temperature and the target temperature in the thermostat, Techniques have been proposed to suppress temperature overshoot.
However, if the temperature of the separation column reaches the column temperature at which the sample is separated in a short time, it is difficult to suppress overshoot. In particular, when the voltage of the power source that supplies power to the heater is selected from an allowable voltage range such as 100 V to 240 V, and further set to any voltage within this allowable voltage range. The difference in temperature control parameters tends to cause a difference in the heat generation status of the heater, which makes it difficult to suppress overshoot.
　本発明の課題は、分離カラムの温度を、オーバーシュートを抑えながら試料の分離を行うカラム温度に短い時間で到達させることのできる安価なガスクロマトグラフ及びそのようなガスクロマトグラフに用いられる温度調節装置を提供することである。
　本発明の他の課題は、高価なガスクロマトグラフを用いなくても、分離カラムの温度を、オーバーシュートを抑えながら試料の分離を行うカラム温度に短い時間で到達させることのできるガスクロマトグラフの温度調節方法を提供することである。 An object of the present invention is to provide an inexpensive gas chromatograph capable of allowing the temperature of a separation column to reach the column temperature for separating a sample in a short time while suppressing overshoot, and a temperature control device used for such a gas chromatograph. Is to provide.
Another object of the present invention is to control the temperature of a gas chromatograph that allows the temperature of a separation column to reach the column temperature for separating a sample in a short time while suppressing overshoot without using an expensive gas chromatograph. Is to provide a method.
　以下に、課題を解決するための手段として複数の態様を説明する。これら態様は、必要に応じて任意に組み合せることができる。
　本発明の一見地に係るガスクロマトグラフは、キャリアガスにより導入される試料を、所定のカラム温度において複数の成分に分離するための分離カラムと、分離カラムを加熱するためのカラムヒータと、分離カラムの温度をカラム温度に調節するための温度調節装置と、を備えている。温度調節装置は、分離カラムの設定温度を指示する設定温度指示部と、分離カラムの温度を測定するための温度測定部と、設定温度指示部が指示する設定温度と温度測定部が測定した温度との温度差に応じて外部電源からカラムヒータに対して出力される電力を制御して分離カラムの温度を設定温度に制御する温度制御部と、を含んでいる。設定温度指示部は、カラム温度に達すまでの間の設定温度変更期間では、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更するものである。
　本発明の一見地に係るガスクロマトグラフでは、設定温度指示部が、カラム温度に達すまでの間の設定温度変更期間では、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更する。したがって、このような制御を行わなければオーバーシュートが発生していた期間では、設定温度がカラム温度よりも低くなる。このように上記期間に設定温度とカラム温度との差分を発生させることで、オーバーシュートを抑制できる。 Hereinafter, a plurality of modes will be described as means for solving the problems. These aspects can be arbitrarily combined as necessary.
A gas chromatograph according to an aspect of the present invention includes a separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature, a column heater for heating the separation column, and a separation column. A temperature adjusting device for adjusting the temperature to the column temperature. The temperature control device includes a set temperature indicating unit for indicating the set temperature of the separation column, a temperature measuring unit for measuring the temperature of the separation column, a set temperature indicated by the set temperature indicating unit, and a temperature measured by the temperature measuring unit. And a temperature control unit that controls the power output from the external power source to the column heater in accordance with the temperature difference between them and controls the temperature of the separation column to a set temperature. The set temperature instructing unit changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature change period until the column temperature is reached.
In the gas chromatograph according to an aspect of the present invention, the set temperature indicating unit changes the set temperature so as to gradually approach the column temperature as time passes during the set temperature changing period until the column temperature is reached. Therefore, if such control is not performed, the set temperature becomes lower than the column temperature during a period in which overshoot occurs. Thus, overshoot can be suppressed by generating the difference between the set temperature and the column temperature in the period.
　上述のガスクロマトグラフにおいて、カラムヒータは、所定の許容電圧範囲から選択された電源電圧を有する外部電源から電力を供給可能に構成されてもよい。温度調節装置は、当該電源電圧を有する外部電源からカラムヒータに対して出力される電力を制御可能に構成されてもよい。
　上述のガスクロマトグラフは、外部電源の電源電圧を検出する電源電圧検出部をさらに備えていてもよい。温度制御部は、電源電圧検出部で検出された電源電圧に応じてパルス幅の設定を変更して外部電源からカラムヒータに対して出力される電力をＰＷＭ制御するように構成されてもよい。
　上述のガスクロマトグラフにおいて、分離カラムは、筒状の樹脂成形品と、樹脂成形品の外面を覆う金属被覆とを有していてもよい。カラムヒータは、金属被覆に密接して配設され、金属被覆を加熱するように構成されてもよい。
　上述のガスクロマトグラフにおいて、設定温度指示部は、設定温度とカラム温度との温度差の変化率が時間経過とともに減少するように設定されていてもよい。 In the gas chromatograph described above, the column heater may be configured to be able to supply power from an external power supply having a power supply voltage selected from a predetermined allowable voltage range. The temperature adjustment device may be configured to be able to control power output to the column heater from an external power supply having the power supply voltage.
The gas chromatograph described above may further include a power supply voltage detection unit that detects the power supply voltage of the external power supply. The temperature control unit may be configured to change the pulse width setting according to the power supply voltage detected by the power supply voltage detection unit and perform PWM control on the power output from the external power supply to the column heater.
In the gas chromatograph described above, the separation column may have a cylindrical resin molded product and a metal coating covering the outer surface of the resin molded product. The column heater may be arranged in close contact with the metal coating and configured to heat the metal coating.
In the gas chromatograph described above, the set temperature instructing unit may be set so that the rate of change of the temperature difference between the set temperature and the column temperature decreases with time.
　本発明の一見地に係るガスクロマトグラフの温度調節装置は、キャリアガスにより導入される試料を、所定のカラム温度において複数の成分に分離するための分離カラムと分離カラムを加熱するためのカラムヒータとを備えるガスクロマトグラフに用いられる。温度調節装置は、分離カラムの温度をカラム温度に調節するための装置である。温度調節装置は、分離カラムの設定温度を指示する設定温度指示部と、分離カラムの温度を測定するための温度測定部と、設定温度指示部が指示する設定温度と温度測定部が測定した温度との温度差に応じて外部電源からカラムヒータに対して出力される電力を制御して分離カラムの温度を設定温度に制御する温度制御部と、を含んでいる。設定温度指示部は、カラム温度に達すまでの間の設定温度変更期間では、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更する。
　本発明の一見地に係るガスクロマトグラフの温度調節装置では、設定温度指示部が、カラム温度に達すまでの間の設定温度変更期間では、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更する。したがって、このような制御を行わなければオーバーシュートが発生しいていた期間では、設定温度がカラム温度よりも低い。このように上記期間に設定温度とカラム温度との差分を発生させることで、オーバーシュートを抑制できる。
　上述の温度調節装置において、カラムヒータは、所定の許容電圧範囲から選択された電源電圧を有する外部電源から電力を供給可能に構成されていてもよい。温度制御部は、外部電源の電源電圧を検出する電源電圧検出部を含み、電源電圧に応じてパルス幅の設定を変更して外部電源からカラムヒータに対して出力される電力をＰＷＭ制御するように構成されてもよい。 A temperature control device for a gas chromatograph according to an aspect of the present invention includes a separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature, and a column heater for heating the separation column. Used for gas chromatographs. The temperature adjusting device is a device for adjusting the temperature of the separation column to the column temperature. The temperature control device includes a set temperature indicating unit for indicating the set temperature of the separation column, a temperature measuring unit for measuring the temperature of the separation column, a set temperature indicated by the set temperature indicating unit, and a temperature measured by the temperature measuring unit. And a temperature control unit that controls the power output from the external power source to the column heater in accordance with the temperature difference between them and controls the temperature of the separation column to a set temperature. The set temperature instruction unit changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature change period until the column temperature is reached.
In the temperature control device for a gas chromatograph according to an aspect of the present invention, the set temperature indicating unit is changed so that the set temperature gradually approaches the column temperature as time passes during the set temperature changing period until the column temperature is reached. To do. Therefore, if such control is not performed, the set temperature is lower than the column temperature during a period in which overshoot has occurred. Thus, overshoot can be suppressed by generating the difference between the set temperature and the column temperature in the period.
In the above-described temperature control apparatus, the column heater may be configured to be able to supply power from an external power supply having a power supply voltage selected from a predetermined allowable voltage range. The temperature control unit includes a power supply voltage detection unit that detects the power supply voltage of the external power supply, and changes the pulse width setting according to the power supply voltage so as to PWM-control the power output from the external power supply to the column heater. It may be configured.
　本発明の一見地に係るガスクロマトグラフの温度調節方法は、キャリアガスにより導入される試料を、所定のカラム温度において複数の成分に分離するための分離カラムと分離カラムを加熱するためのカラムヒータとを備えるガスクロマトグラフに用いられる。温度調節方法は、分離カラムの温度をカラム温度に調節する方法である。温度調節方法は、分離カラムの設定温度を指示する設定温度指示ステップと、分離カラムの温度を測定する温度測定ステップと、設定温度指示ステップで指示された設定温度と温度測定ステップで測定された温度との温度差に応じて外部電源からカラムヒータに対して出力される電力を制御して分離カラムの温度を設定温度に制御する温度制御ステップと、を含んでいる。設定温度指示ステップでは、カラム温度に達すまでの間の設定温度変更期間では、設定温度が時間経過に従って徐々にカラム温度に近づくように変更されるものである。
　本発明の一見地に係るガスクロマトグラフの温度調節方法では、設定温度指示ステップで、カラム温度に達すまでの間の設定温度変更期間では、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更する。したがって、このような制御を行わなければオーバーシュートが発生していた期間では、設定温度がカラム温度よりも低くなる。このように上記期間に設定温度とカラム温度との差分を発生させることで、オーバーシュートを抑制できる。 A gas chromatograph temperature control method according to an aspect of the present invention includes a separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature, and a column heater for heating the separation column. Used for gas chromatographs. The temperature adjustment method is a method of adjusting the temperature of the separation column to the column temperature. The temperature adjustment method includes a set temperature indicating step for indicating the set temperature of the separation column, a temperature measuring step for measuring the temperature of the separation column, a set temperature indicated in the set temperature indicating step, and a temperature measured in the temperature measuring step. And a temperature control step of controlling the power output from the external power source to the column heater in accordance with the temperature difference between the separation column and the temperature of the separation column to a set temperature. In the set temperature instruction step, the set temperature is changed so as to gradually approach the column temperature as time elapses in the set temperature change period until the column temperature is reached.
In the gas chromatograph temperature adjustment method according to an aspect of the present invention, the set temperature is changed so that the set temperature gradually approaches the column temperature as time elapses in the set temperature indication step until the column temperature is reached. To do. Therefore, if such control is not performed, the set temperature becomes lower than the column temperature during a period in which overshoot occurs. Thus, overshoot can be suppressed by generating the difference between the set temperature and the column temperature in the period.
　本発明のガスクロマトグラフ又はガスクロマトグラフの温度調節装置によれば、分離カラムの温度を、オーバーシュートを抑えながらカラム温度に短い時間で到達させることができる。
　本発明のガスクロマトグラフの温度調節方法によれば、安価なガスクロマトグラフであっても、分離カラムの温度を、オーバーシュートを抑えながらカラム温度に短い時間で到達させることができる。 According to the gas chromatograph or the gas chromatograph temperature control apparatus of the present invention, the temperature of the separation column can be reached in a short time while suppressing overshoot.
According to the gas chromatograph temperature adjustment method of the present invention, the temperature of the separation column can be reached in a short time while suppressing overshoot even with an inexpensive gas chromatograph.
本発明の実施形態に係るガスクロマトグラフの構成の一例を示す概念図。The conceptual diagram which shows an example of a structure of the gas chromatograph which concerns on embodiment of this invention. 図１のガスクロマトグラフで用いられる分離カラムの一例を示す平面図。The top view which shows an example of the separation column used with the gas chromatograph of FIG. 図２の分離カラムにカラムヒータが巻きつけられた状態を示す平面図。The top view which shows the state by which the column heater was wound around the separation column of FIG. 図３のＩ－Ｉ線で切断した断面の構造を示す模式図。FIG. 4 is a schematic diagram showing a cross-sectional structure cut along a line II in FIG. 3. 図３の分離カラムにさらに保温材が巻きつけられた状態を示す平面図。The top view which shows the state by which the heat insulating material was wound around the separation column of FIG. 図１のガスクロマトグラフで用いられるガスセンサの一例を示す概念図。The conceptual diagram which shows an example of the gas sensor used with the gas chromatograph of FIG. 図１のガスクロマトグラフの構成を説明するためのブロック図。The block diagram for demonstrating the structure of the gas chromatograph of FIG. 図１のガスクロマトグラフで用いられる温度調節装置の構成の一例を説明するためのブロック図。The block diagram for demonstrating an example of a structure of the temperature control apparatus used with the gas chromatograph of FIG. （ａ）ＰＷＭ制御回路の内部で発生される三角波の波形図、（ｂ）外部電源の電源電圧が高い場合のＰＷＭ信号の一例を示す波形図、（ｃ）外部電源の電源電圧が低い場合のＰＷＭ信号の一例を示す波形図、（ｄ）外部電源の電源電圧が高い場合にカラムヒータに印加される電圧波形の一例を示す波形図、（ｅ）外部電源の電源電圧が低い場合にカラムヒータに印加される電圧波形の一例を示す波形図。(A) A waveform diagram of a triangular wave generated inside the PWM control circuit, (b) a waveform diagram showing an example of a PWM signal when the power supply voltage of the external power supply is high, and (c) a case where the power supply voltage of the external power supply is low Waveform diagram showing an example of a PWM signal, (d) Waveform diagram showing an example of a voltage waveform applied to the column heater when the power supply voltage of the external power supply is high, (e) Application to the column heater when the power supply voltage of the external power supply is low The wave form diagram which shows an example of the voltage waveform performed. 外部電源の電源電圧が高い場合に設定温度を一定としたときの分離カラムの温度の変化を示すグラフ。The graph which shows the change of the temperature of a separation column when setting temperature is constant when the power supply voltage of an external power supply is high. 外部電源の電源電圧が低い場合に設定温度を一定としたときの分離カラムの温度の変化を示すグラフ。The graph which shows the change of the temperature of a separation column when setting temperature is constant when the power supply voltage of an external power supply is low. 外部電源の電源電圧が高い場合に設定温度をカラム温度に徐々に近づけたときの分離カラムの温度の変化を示すグラフ。The graph which shows the change of the temperature of a separation column when setting temperature is brought close to column temperature gradually when the power supply voltage of an external power supply is high. 外部電源の電源電圧が低い場合に設定温度をカラム温度に徐々に近づけたときの分離カラムの温度の変化を示すグラフ。The graph which shows the change of the temperature of a separation column when setting temperature is made to approach column temperature gradually when the power supply voltage of an external power supply is low. 設定温度を変化させる関数の一例を説明するためのグラフ。The graph for demonstrating an example of the function which changes preset temperature.
　本発明の一実施形態に係るガスクロマトグラフ及びその温度調節装置について図面を用いて説明する。
　（１）ガスクロマトグラフの構成の概要
　図１に示されているように、ガスクロマトグラフ１０は、エアポンプ１１とガス浄化装置１２と流量調整器１３と流量センサ１４と分離カラム１５と半導体ガスセンサ１６とカラムヒータ２０と温度調節装置３０とを備えている。温度調節装置３０を構成する部品の多くは、制御基板５０に実装されている。分離カラム１５と半導体ガスセンサ１６とカラムヒータ２０とは、センサカラムブロック６０に含まれている。温度調節装置３０を構成する部品のうちの一つである制御サーミスタ３３は、センサカラムブロック６０に含まれている。制御サーミスタ３３は、例えばＮＴＣサーミスタである。
　ガスクロマトグラフ１０のキャリアガスは、空気である。エアポンプ１１は、キャリアガスとしての空気をガスクロマトグラフ１０に流す装置である。ガス浄化装置１２は、キャリアガスを浄化する装置であり、キャリアガスを浄化するために例えばガス吸着剤やガス分解触媒を備えている。ガス吸着剤は、例えば活性炭やシリカゲルである。また、ガス分解触媒は、酸化触媒である。 A gas chromatograph and a temperature control device thereof according to an embodiment of the present invention will be described with reference to the drawings.
(1) Outline of configuration of gas chromatograph As shown in FIG. 1, the gas chromatograph 10 includes an air pump 11, a gas purification device 12, a flow rate regulator 13, a flow rate sensor 14, a separation column 15, a semiconductor gas sensor 16, and a column heater. 20 and a temperature control device 30. Many of the components constituting the temperature adjustment device 30 are mounted on the control board 50. The separation column 15, the semiconductor gas sensor 16, and the column heater 20 are included in the sensor column block 60. A control thermistor 33, which is one of the components constituting the temperature adjustment device 30, is included in the sensor column block 60. The control thermistor 33 is, for example, an NTC thermistor.
The carrier gas of the gas chromatograph 10 is air. The air pump 11 is a device for flowing air as a carrier gas to the gas chromatograph 10. The gas purification device 12 is a device that purifies the carrier gas, and includes, for example, a gas adsorbent and a gas decomposition catalyst in order to purify the carrier gas. The gas adsorbent is, for example, activated carbon or silica gel. The gas decomposition catalyst is an oxidation catalyst.
　流量調整器１３は、分離カラム１５に送られるキャリアガスの流量が一定量になるように調整する。流量調整器１３には、例えば所定の範囲で流量が弁開度に比例する特性を有するリニアバルブが用いられる。流量センサ１４は、分離カラム１５に送られるキャリアガスの流量を測定する。
　分離カラム１５は、キャリアガスにより導入される試料を、所定のカラム温度において複数の成分に分離する筒状の器材である。ここでは、分離カラム１５が充填カラムである場合について説明するが、分離カラム１５にキャピラリーカラムを使用してもよい。分離カラム１５の上流側には、試料を導入するための試料導入部１７が設けられている。
　半導体ガスセンサ１６は、分離カラム１５の下流側に配置され、分離カラム１５を通過してきた試料の成分を検知する。半導体ガスセンサ１６は、例えば、後述するような半導体センサである。
　分離カラム１５は、例えば所定のカラム温度で試料の分離を行う。分離カラム１５を所定のカラム温度にするために、分離カラム１５にはカラムヒータ２０が取り付けられている。カラムヒータ２０は、面状発熱体であるラバーヒータである。カラムヒータ２０の温度は、温度調節装置３０によって調節される。 The flow rate adjuster 13 adjusts the flow rate of the carrier gas sent to the separation column 15 to be a constant amount. As the flow rate regulator 13, for example, a linear valve having a characteristic that the flow rate is proportional to the valve opening within a predetermined range is used. The flow sensor 14 measures the flow rate of the carrier gas sent to the separation column 15.
The separation column 15 is a cylindrical device that separates a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature. Here, although the case where the separation column 15 is a packed column will be described, a capillary column may be used as the separation column 15. A sample introduction part 17 for introducing a sample is provided on the upstream side of the separation column 15.
The semiconductor gas sensor 16 is disposed on the downstream side of the separation column 15 and detects the component of the sample that has passed through the separation column 15. The semiconductor gas sensor 16 is a semiconductor sensor as described later, for example.
For example, the separation column 15 separates the sample at a predetermined column temperature. In order to set the separation column 15 to a predetermined column temperature, a column heater 20 is attached to the separation column 15. The column heater 20 is a rubber heater that is a planar heating element. The temperature of the column heater 20 is adjusted by the temperature adjustment device 30.
　（２）分離カラム周辺の構成
　図２から図５を用いて、分離カラム１５の周辺の構成について説明する。図２には、分離カラム１５の外観が示されている。図３には、分離カラム１５にカラムヒータ２０が巻きつけられた状態が示されている。図４は、図３のＩ－Ｉ線で切断した断面の模式図である。
　分離カラム１５は、円筒状の樹脂成形品１５ａ（図４）と、樹脂成形品１５ａの外面を覆う金属被覆１５ｂを有している。樹脂成形品１５ａは、例えばポリフッ化エチレン樹脂、さらに詳しくは例えばポリテトラフルオロエチレンで形成される。金属被覆１５ｂは、例えば銅管又は銅箔を用いて形成される。
　図４に示すように、円筒状の樹脂成形品１５ａの内部には、固定相を形成する充填材１５ｃが充填されている。充填材１５ｃは、例えば珪藻土、モレキュラシーブ、ポーラスポリマー、又はアルミナである。また、固定相を形成するために、充填材１５ｃには液相がコーティングさせていてもよい。
　図３に示すように、分離カラム１５の長手方向の中央部分に測定サーミスタ３２と制御サーミスタ３３が結束バンド３１によって取り付けられている。測定サーミスタ３２と制御サーミスタ３３の両側の位置に温度ヒューズ３４が取り付けられている。
　図５に示すように、カラムヒータ２０が巻きつけられている分離カラム１５の上には、さらに保温材３５が巻きつけられている。保温材３５は、例えば発泡ウレタンシートである。 (2) Configuration around the separation column The configuration around the separation column 15 will be described with reference to FIGS. FIG. 2 shows the appearance of the separation column 15. FIG. 3 shows a state in which the column heater 20 is wound around the separation column 15. FIG. 4 is a schematic view of a cross section taken along the line II of FIG.
The separation column 15 has a cylindrical resin molded product 15a (FIG. 4) and a metal coating 15b that covers the outer surface of the resin molded product 15a. The resin molded product 15a is made of, for example, a polyfluorinated ethylene resin, more specifically, for example, polytetrafluoroethylene. The metal coating 15b is formed using, for example, a copper tube or a copper foil.
As shown in FIG. 4, a cylindrical resin molded product 15a is filled with a filler 15c that forms a stationary phase. The filler 15c is, for example, diatomaceous earth, molecular sieve, porous polymer, or alumina. Moreover, in order to form a stationary phase, the filler 15c may be coated with a liquid phase.
As shown in FIG. 3, a measurement thermistor 32 and a control thermistor 33 are attached to a central portion in the longitudinal direction of the separation column 15 by a binding band 31. Thermal fuses 34 are attached to positions on both sides of the measurement thermistor 32 and the control thermistor 33.
As shown in FIG. 5, a heat insulating material 35 is further wound on the separation column 15 around which the column heater 20 is wound. The heat insulating material 35 is, for example, a foamed urethane sheet.
　（３）半導体ガスセンサ１６
　図６は、図１のガスクロマトグラフ１０で用いられるガスセンサの一例として半導体ガスセンサ１６を示す概念図である。図６には、半導体ガスセンサ１６は、金属酸化物半導体を主成分とする感ガス体１６ａと、感ガス体１６ａ中に埋設したコイル状のヒータ兼用電極１６ｂと、ヒータ兼用電極１６ｂのコイルの中心又はその近傍を貫通するように感ガス体１６ａ中に埋設した半導体抵抗検出用電極１６ｃと、電極パッド１６ｄ，１６ｅとを備えている。ヒータ兼用電極１６ｂの両端は２つの電極パッド１６ｄに接続されている。半導体抵抗検出用電極１６ｃは電極パッド１６ｅに接続されている。電極パッド６１ｄ，１６ｅは、ヒータ兼用電極１６ｂと半導体抵抗検出用電極１６ｃとの間の負荷抵抗の変化を取り出すために用いられる。
　半導体ガスセンサ１６は、感ガス体１６ａの抵抗値の変化に基づいて検知対象のガス成分を検出する。検知対象のガス成分としては、例えば口臭の要因となる揮発性硫化物（ＶＳＣ：Volatile Sulphur Compounds）があり、ＶＳＣとしては例えば、硫化水素、メチルメルカプタン、エチルメルカプタン及びジメチルサルファイドがある。感ガス体１６ａを形成する金属酸化物としては、例えば、ＳｎＯ２、Ｉｎ２Ｏ３、ＺｎＯ、ＷＯ３が挙げられる。 (3) Semiconductor gas sensor 16
FIG. 6 is a conceptual diagram showing a semiconductor gas sensor 16 as an example of a gas sensor used in the gas chromatograph 10 of FIG. In FIG. 6, a semiconductor gas sensor 16 includes a gas sensitive body 16a mainly composed of a metal oxide semiconductor, a coiled heater combined electrode 16b embedded in the gas sensitive body 16a, and the center of the coil of the heater combined electrode 16b. Alternatively, a semiconductor resistance detection electrode 16c embedded in the gas sensitive body 16a so as to penetrate the vicinity thereof, and electrode pads 16d and 16e are provided. Both ends of the heater combined electrode 16b are connected to two electrode pads 16d. The semiconductor resistance detection electrode 16c is connected to the electrode pad 16e. The electrode pads 61d and 16e are used for taking out a change in load resistance between the heater electrode 16b and the semiconductor resistance detection electrode 16c.
The semiconductor gas sensor 16 detects a gas component to be detected based on a change in the resistance value of the gas sensitive body 16a. Examples of gas components to be detected include volatile sulfides (VSC) that cause bad breath, and examples of VSCs include hydrogen sulfide, methyl mercaptan, ethyl mercaptan, and dimethyl sulfide. Examples of the metal oxide that forms the gas sensitive body 16a include SnO 2 , In 2 O 3 , ZnO, and WO 3 .
　（４）温度調節装置３０の周辺の構成
　図７は、温度調節装置３０及びその周辺の構成を説明するためのガスクロマトグラフ１０のブロック図である。図７には、図１に示されているエアポンプ１１とガス浄化装置１２と流量調整器１３と流量センサ１４と半導体ガスセンサ１６とカラムヒータ２０と温度調節装置３０とが示されている。また、制御基板５０及び、分離カラム１５（図１参照）を含むセンサカラムブロック６０が示されている。
　制御基板５０には、各種のスイッチ（図示せず）並びに、ガスクロマトグラフ１０の動作状態を報知するためのパワーLED７１、エラーLED７２、レディーLED７３及びブザー７４が実装されているスイッチ・LED基板７０が接続されている。また、制御基板５０には、制御基板５０との間で送受信されるデータを記憶したり、表示画面８１に表示したりするためのパーソナルコンピュータ８０が接続されている。さらに、制御基板５０には、外部電源１００が接続されている。制御基板５０に接続可能な外部電源１００としては、例えば９０Ｖから２６４Ｖまでの許容電圧範囲より選択された電源電圧を有する商用交流電源である。日本では、例えば単相１００Ｖ又は単相２００Ｖの交流電源が接続される。 (4) Configuration around the temperature control device 30 FIG. 7 is a block diagram of the gas chromatograph 10 for explaining the temperature control device 30 and the configuration around it. 7 shows the air pump 11, the gas purification device 12, the flow rate regulator 13, the flow rate sensor 14, the semiconductor gas sensor 16, the column heater 20, and the temperature adjustment device 30 shown in FIG. Also shown is a sensor column block 60 including a control substrate 50 and a separation column 15 (see FIG. 1).
Connected to the control board 50 are various switches (not shown) and a switch / LED board 70 on which a power LED 71, an error LED 72, a ready LED 73, and a buzzer 74 for notifying the operation state of the gas chromatograph 10 are mounted. Has been. The control board 50 is connected to a personal computer 80 for storing data transmitted to and received from the control board 50 and displaying the data on the display screen 81. Furthermore, an external power supply 100 is connected to the control board 50. The external power supply 100 that can be connected to the control board 50 is a commercial AC power supply having a power supply voltage selected from an allowable voltage range of 90 V to 264 V, for example. In Japan, for example, a single-phase 100V or single-phase 200V AC power supply is connected.
　パワーLED７１は、外部電源１００に接続されたときに点灯する。レディーLED７３は、ガスクロマトグラフ１０が測定可能な状態になったときに点灯する。エラーLED７２は、ガスクロマトグラフ１０が誤動作したときに点灯する。
　制御基板５０には、さらに、アナログデジタル変換部５１とＶＨ制御部５２とリニアバルブ制御部５３とＤＣ電圧制御部５４とが実装されている。また、制御基板５０には、温度調節装置３０を構成する部品として、中央演算装置（ＣＰＵ）３８と、電源電圧検出部３６と、温度制御部３７と、ゼロクロス半導体リレー（以下、ＺＣＳＳＲという）３９とが実装されている。
　アナログデジタル変換部（Ａ/Ｄ変換部）５１は、電極パッド１６ｄ，１６ｅに接続されている。ヒータ兼用電極１６ｂをヒータとして機能させない期間において、ヒータ兼用電極１６ｂと半導体抵抗検出用電極１６ｃとの間の負荷抵抗を測定することを目的として、アナログデジタル変換部５１は、感ガス体１６ａの抵抗値に応じて変化する半導体ガスセンサ１６の出力電圧をデジタル信号に変換して温度調節装置３０のＣＰＵ３８に出力する。
　ＶＨ制御部５２は、半導体ガスセンサ１６の２つの電極パッド１６ｄに接続されており、ヒータ兼用電極１６ｂに印加する電圧を制御して感ガス体１６ａの温度を制御する。 The power LED 71 is lit when connected to the external power supply 100. The ready LED 73 is lit when the gas chromatograph 10 becomes measurable. The error LED 72 is lit when the gas chromatograph 10 malfunctions.
The control board 50 further includes an analog-digital conversion unit 51, a VH control unit 52, a linear valve control unit 53, and a DC voltage control unit 54. The control board 50 includes a central processing unit (CPU) 38, a power supply voltage detection unit 36, a temperature control unit 37, and a zero-cross semiconductor relay (hereinafter referred to as ZCSSR) 39 as components constituting the temperature adjustment device 30. And have been implemented.
The analog / digital converter (A / D converter) 51 is connected to the electrode pads 16d and 16e. For the purpose of measuring the load resistance between the heater serving electrode 16b and the semiconductor resistance detecting electrode 16c during the period in which the heater serving electrode 16b does not function as a heater, the analog-to-digital conversion unit 51 performs the resistance of the gas sensitive body 16a. The output voltage of the semiconductor gas sensor 16 that changes according to the value is converted into a digital signal and output to the CPU 38 of the temperature control device 30.
The VH controller 52 is connected to the two electrode pads 16d of the semiconductor gas sensor 16, and controls the temperature of the gas sensitive body 16a by controlling the voltage applied to the heater electrode 16b.
　（４－１）温度調節装置３０の構成
　温度調節装置３０は、分離カラム１５の温度をカラム温度に調節する装置である。図８に示されているように、温度調節装置３０は、制御サーミスタ３３と、電源電圧検出部３６と、温度制御部３７と、ＣＰＵ３８と、ＺＣＳＳＲ３９と、抵抗４４とを備えている。また、温度調節装置３０の温度制御部３７は、比例積分制御回路（以下、ＰＩ制御回路という）４１と、ＰＷＭ制御回路４２と、サーミスタ断線検知回路４３とを備えている。さらに、ＣＰＵ３８は、ソフトウェアの実行によって設定温度指示部３８ａを形成する。設定温度指示部３８ａは、分離カラム１５の設定温度を指示する。
　温度制御部３７のＰＩ制御回路４１には、制御サーミスタ３３とＣＰＵ３８が接続されている。制御サーミスタ３３は、分離カラム１５の温度を測定するための温度測定部である。温度制御部３７は、設定温度指示部３８ａが指示する設定温度と制御サーミスタ３３が測定した温度との温度差に応じて外部電源１００からカラムヒータ２０に対して出力される電力を制御して分離カラム１５の温度を設定温度に制御する機能を有している。ＰＩ制御回路４１は、ＣＰＵ３８の設定温度指示部３８ａが指示する設定温度と制御サーミスタ３３によって測定された分離カラム１５の温度とを比較して、比較された設定温度と分離カラム１５の温度との温度差に応じた出力電圧ＯＶを出力する。 (4-1) Configuration of Temperature Control Device 30 The temperature control device 30 is a device that adjusts the temperature of the separation column 15 to the column temperature. As shown in FIG. 8, the temperature adjustment device 30 includes a control thermistor 33, a power supply voltage detection unit 36, a temperature control unit 37, a CPU 38, a ZCSSR 39, and a resistor 44. The temperature control unit 37 of the temperature adjustment device 30 includes a proportional-integral control circuit (hereinafter referred to as a PI control circuit) 41, a PWM control circuit 42, and a thermistor disconnection detection circuit 43. Further, the CPU 38 forms a set temperature instruction unit 38a by executing software. The set temperature instruction unit 38 a instructs the set temperature of the separation column 15.
A control thermistor 33 and a CPU 38 are connected to the PI control circuit 41 of the temperature control unit 37. The control thermistor 33 is a temperature measurement unit for measuring the temperature of the separation column 15. The temperature control unit 37 controls the power output from the external power source 100 to the column heater 20 according to the temperature difference between the set temperature indicated by the set temperature indicating unit 38a and the temperature measured by the control thermistor 33, thereby separating the separation column. 15 has a function of controlling the temperature of 15 to the set temperature. The PI control circuit 41 compares the set temperature indicated by the set temperature indicating unit 38a of the CPU 38 with the temperature of the separation column 15 measured by the control thermistor 33, and compares the set temperature thus compared with the temperature of the separation column 15. An output voltage OV corresponding to the temperature difference is output.
　また、ＰＩ制御回路４１には、電源電圧検出部３６も接続されている。電源電圧検出部３６は、外部電源１００の電源電圧が、許容電圧範囲の中央近傍の値以上か、中央近傍の値よりも小さいかを判断して、その判断結果を出力する。例えば許容電圧範囲が９０Ｖから２６４Ｖまでの範囲であれば例えば許容電圧範囲の中央近傍の値が１３０Ｖ～２００Ｖの間から選択された値になる。ここで、中央近傍の値が１６０Ｖであるとすると、外部電源１００が１００Ｖのときに電源電圧検出部３６が「Ｌｏｗ」を出力し、外部電源１００が２００Ｖのときに電源電圧検出部３６が「Ｈｉｇｈ」を出力する。
　ＰＩ制御回路４１は、電源電圧検出部３６が「Ｌｏｗ」を出力したときの出力電圧ＯＶ１の変動範囲ＲＯＶ１よりも、電源電圧検出部３６が「Ｈｉｇｈ」を出力したときの出力電圧ＯＶ２の変動範囲ＲＯＶ２が小さくなるように設定されている（図９（ａ）参照）。 A power supply voltage detection unit 36 is also connected to the PI control circuit 41. The power supply voltage detector 36 determines whether the power supply voltage of the external power supply 100 is greater than or equal to the value near the center of the allowable voltage range or smaller than the value near the center, and outputs the determination result. For example, if the allowable voltage range is from 90V to 264V, for example, the value near the center of the allowable voltage range is a value selected from 130V to 200V. Here, assuming that the value in the vicinity of the center is 160 V, the power supply voltage detection unit 36 outputs “Low” when the external power supply 100 is 100 V, and the power supply voltage detection unit 36 outputs “Low” when the external power supply 100 is 200 V. “High” is output.
The PI control circuit 41 has a fluctuation range of the output voltage OV2 when the power supply voltage detection unit 36 outputs “High” rather than a fluctuation range ROV1 of the output voltage OV1 when the power supply voltage detection unit 36 outputs “Low”. ROV2 is set to be small (see FIG. 9A).
　ＰＷＭ制御回路４２は、ＰＩ制御回路４１の出力電圧ＯＶに応じた長さのパルス信号ＰＳをＺＣＳＳＲ３９に出力する。
　温度調節装置３０のＺＣＳＳＲ３９の２つの端子の間には、カラムヒータ２０と外部電源１００が直列に接続されている。ＺＣＳＳＲ３９がオンすると外部電源１００からカラムヒータ２０で電力が供給され、ＺＣＳＳＲ３９がオフすると外部電源１００からカラムヒータ２０への電力の供給が停止される。
　このＺＣＳＳＲ３９は、ノイズを低減して半導体ガスセンサ１６の検出精度を向上させるために、外部電源１００の交流電圧がゼロ電圧付近の時点でトリガを掛けるためのゼロクロス回路を内蔵している。従って、ＰＷＭ制御回路４２のパルス信号ＰＳが出力されてから始めてのゼロ電圧でカラムヒータ２０に外部電源１００の電圧の印加を開始し、パルス信号ＰＳの出力が終わってから始めてのゼロ電圧でカラムヒータ２０に外部電源１００の電圧の印加を停止する。 The PWM control circuit 42 outputs a pulse signal PS having a length corresponding to the output voltage OV of the PI control circuit 41 to the ZCSSR 39.
The column heater 20 and the external power supply 100 are connected in series between the two terminals of the ZCSSR 39 of the temperature control device 30. When the ZCSSR 39 is turned on, power is supplied from the external power supply 100 by the column heater 20, and when the ZCCSR 39 is turned off, the supply of power from the external power supply 100 to the column heater 20 is stopped.
In order to reduce noise and improve the detection accuracy of the semiconductor gas sensor 16, the ZCCSR 39 has a built-in zero cross circuit for triggering when the AC voltage of the external power supply 100 is near zero voltage. Therefore, the application of the voltage of the external power supply 100 to the column heater 20 is started at the first zero voltage after the pulse signal PS of the PWM control circuit 42 is output, and the column heater 20 is started at the first zero voltage after the output of the pulse signal PS is finished. The application of the voltage of the external power supply 100 is stopped.
　（４－２）温度調節装置３０の動作
　図９（ａ）に示されているように、ＰＷＭ制御回路４２の内部で、三角波ＴＷの形状を呈する電圧が発生されている。三角波ＴＷの周期が例えば１２０ｍｓであるとすると、ＰＷＭ制御回路４２の発生するＰＷＭ信号の周期は１２０ｍｓになる。
　設定温度と分離カラム１５の温度との温度差がないか又は設定温度以上に分離カラム１５の温度が高いときには、出力電圧ＯＶが０Ｖになる。ＰＷＭ制御回路４２は、ＰＩ制御回路４１の出力電圧ＯＶが０Ｖのときは、ＰＷＭ信号が出力されない。図９（ａ）及び図９（ｃ）に示されているように、電源電圧検出部３６が「Ｌｏｗ」を出力したときの出力電圧ＯＶ１の変動範囲ＲＯＶ１の上限値が入力されているときには、三角波ＴＷの電圧がその上限値以下になっている期間だけＰＷＭ信号Ｐ１が出力される。例えば、外部電源１００の電源電圧が１００ＶのときのＰＷＭ信号Ｐ１の最大値（デューティー）は８０ｍｓに設定されている。それに対して、図９（ａ）及び図９（ｂ）に示されているように、電源電圧検出部３６が「Ｈｉｇｈ」を出力したときの出力電圧ＯＶ２の変動範囲ＲＯＶ２の上限値が入力されているときには、三角波ＴＷの電圧がその上限値以下になっている期間だけＰＷＭ信号Ｐ２が出力される。例えば、外部電源１００の電源電圧が２００ＶのときのＰＷＭ信号Ｐ１の最大値（デューティー）は２０ｍｓに設定されている。 (4-2) Operation of Temperature Control Device 30 As shown in FIG. 9A, a voltage having the shape of a triangular wave TW is generated inside the PWM control circuit. If the period of the triangular wave TW is 120 ms, for example, the period of the PWM signal generated by the PWM control circuit 42 is 120 ms.
When there is no temperature difference between the set temperature and the temperature of the separation column 15 or when the temperature of the separation column 15 is higher than the set temperature, the output voltage OV becomes 0V. The PWM control circuit 42 does not output a PWM signal when the output voltage OV of the PI control circuit 41 is 0V. As shown in FIGS. 9A and 9C, when the upper limit value of the fluctuation range ROV1 of the output voltage OV1 when the power supply voltage detector 36 outputs “Low” is input, The PWM signal P1 is output only during the period when the voltage of the triangular wave TW is below the upper limit value. For example, the maximum value (duty) of the PWM signal P1 when the power supply voltage of the external power supply 100 is 100 V is set to 80 ms. On the other hand, as shown in FIGS. 9A and 9B, the upper limit value of the fluctuation range ROV2 of the output voltage OV2 when the power supply voltage detection unit 36 outputs “High” is input. When the voltage of the triangular wave TW is lower than the upper limit value, the PWM signal P2 is output. For example, the maximum value (duty) of the PWM signal P1 when the power supply voltage of the external power supply 100 is 200 V is set to 20 ms.
　その結果、図９（ｄ）に示されているように、外部電源１００の電源電圧が高い（例えば、２００Ｖ）場合には、カラムヒータ２０に印加される電圧が高い反面、外部電源１００から供給される時間が短くなる。また、図９（ｅ）に示されているように、外部電源１００の電源電圧が低い場合（例えば、１００Ｖ）には、カラムヒータ２０に印加される電圧が低い反面、外部電源１００から供給される時間が長くなる。このように、外部電源１００の電源電圧が大きく異なる場合でも、カラムヒータ２０に供給される最大電力が近い値になるように調節される。なお、図９（ｄ）及び図９（ｅ）において、実線で示されている波形がカラムヒータ２０に印加される電圧の波形になる。 As a result, as shown in FIG. 9D, when the power supply voltage of the external power supply 100 is high (for example, 200 V), the voltage applied to the column heater 20 is high, but supplied from the external power supply 100. The time required for this is shortened. As shown in FIG. 9E, when the power supply voltage of the external power supply 100 is low (for example, 100 V), the voltage applied to the column heater 20 is low, but supplied from the external power supply 100. The time will be longer. Thus, even when the power supply voltage of the external power supply 100 is greatly different, the maximum power supplied to the column heater 20 is adjusted to a close value. In FIG. 9D and FIG. 9E, the waveform indicated by the solid line is the waveform of the voltage applied to the column heater 20.
　（４－３）設定温度を一定にした場合と徐々にカラム温度に近づけた場合の比較
　（４－３－１）設定温度を一定値に固定した場合（比較例）
　図１０及び図１１には、設定温度指示部３８ａがカラム温度（例えば、３５℃）に設定温度が固定されている場合の分離カラム１５の測定温度の経時変化が示されている。図１０は、外部電源１００の電源電圧が２６４Ｖの場合の分離カラム１５の測定温度を示すグラフであり、図１１は、外部電源１００の電源電圧が９０Ｖの場合の分離カラム１５の測定温度を示すグラフである。これらの測定を行ったときの雰囲気温度は、１０℃である。
　ガスクロマトグラフ１０は、例えば、医療現場や学校の実験室での用途に適するように３０分以内の短時間で、分離カラム１５の温度が、測定に必要なカラム温度に安定するように設定される。このような用途を想定して、電源電圧が９０Ｖであってつまり比較的温度が上がり難い場合でも、３０分以内に分離カラム１５の温度が、測定に必要なカラム温度に安定するように設定されている。したがって、電源電圧が２６４Ｖであってつまり比較的温度が上がり易い場合には、分離カラム１５の温度が大きくオーバーシュートしている。 (4-3) Comparison between the case where the set temperature is made constant and gradually approaching the column temperature (4-3-1) Case where the set temperature is fixed at a constant value (comparative example)
10 and 11 show the change over time in the measured temperature of the separation column 15 when the set temperature instruction section 38a is fixed at the column temperature (for example, 35 ° C.). FIG. 10 is a graph showing the measured temperature of the separation column 15 when the power supply voltage of the external power supply 100 is 264V, and FIG. 11 shows the measured temperature of the separation column 15 when the power supply voltage of the external power supply 100 is 90V. It is a graph. The atmospheric temperature when these measurements are performed is 10 ° C.
The gas chromatograph 10 is set so that the temperature of the separation column 15 is stabilized at the column temperature necessary for measurement in a short time within 30 minutes so as to be suitable for use in, for example, a medical field or a school laboratory. . Assuming such an application, even when the power supply voltage is 90 V, that is, when the temperature is relatively difficult to rise, the temperature of the separation column 15 is set to be stable to the column temperature necessary for measurement within 30 minutes. ing. Therefore, when the power supply voltage is 264 V, that is, when the temperature is relatively easy to rise, the temperature of the separation column 15 greatly overshoots.
　（４－３－２）設定温度を徐々にカラム温度に近づけた場合（実施例）
　図１２及び図１３には、設定温度指示部３８ａがカラム温度例えば３５℃に設定温度を徐々に近づけた場合の分離カラム１５の測定温度の経時変化が示されている。図１２は、外部電源１００の電源電圧が２６４Ｖの場合の分離カラム１５の測定温度を示すグラフであり、図１３は、外部電源１００の電源電圧が９０Ｖの場合の分離カラム１５の測定温度を示すグラフである。図１２及び図１３では、太線が温度であり、細線が設定温度指示部３８ａからの制御出力である。
　設定温度指示部３８ａは、設定温度変更期間Ｓｔでは、設定温度を徐々にカラム温度に近づける。例えば、図１４に示されているような双曲線関数ｆ（λ，ｘ）＝カラム温度＊tanh｛λ＊（ｘ／Ｓｔ）／２｝を用いる。この双曲線関数ｆの値が設定温度になる。ここで、λは、実験を通じて適当に選ばれる定数であり、ｘは時間（ｓｅｃ）の変数である。９分間の設定温度変更期間Ｓｔで、設定温度をカラム温度の近傍まで変化するようにするには、例えば、λ＝４とすれば、ｘ＝５４０のときに、ｆ≒カラム温度×０．９６になる。この場合、例えば、４分３０秒が経過した時点では、ｆ≒カラム温度×０．７５になる。 (4-3-2) When the set temperature is gradually brought close to the column temperature (Example)
12 and 13 show changes with time in the measurement temperature of the separation column 15 when the set temperature instruction unit 38a gradually brings the set temperature close to the column temperature, for example, 35 ° C. FIG. 12 is a graph showing the measured temperature of the separation column 15 when the power supply voltage of the external power supply 100 is 264V, and FIG. 13 shows the measured temperature of the separation column 15 when the power supply voltage of the external power supply 100 is 90V. It is a graph. 12 and 13, the thick line is the temperature, and the thin line is the control output from the set temperature instruction unit 38a.
The set temperature instruction unit 38a gradually brings the set temperature closer to the column temperature during the set temperature change period St. For example, a hyperbolic function f (λ, x) = column temperature * tanh {λ * (x / St) / 2} as shown in FIG. 14 is used. The value of this hyperbolic function f becomes the set temperature. Here, λ is a constant appropriately selected through experiments, and x is a time (sec) variable. In order to change the set temperature to the vicinity of the column temperature in the set temperature change period St of 9 minutes, for example, when λ = 4, when x = 540, f≈column temperature × 0.96 become. In this case, for example, when 4 minutes and 30 seconds have elapsed, f≈column temperature × 0.75.
　なお、設定温度変更期間Ｓｔがカラムヒータ２０の加熱の初期から設定されていることは必要なく、例えば、初期期間Ｂｔには、雰囲気温度からカラム温度に達するのに必要な熱量の６０％に相当する電力量を与えるようにしてもよい。この場合には、ＰＷＭ制御を行わずに外部電源１００の電源電圧を印加する。例えば、２６４Ｖの外部電源１００の場合は１分半ほどの初期期間Ｂｔだけ外部電源１００をカラムヒータ２０に直結し、９０Ｖの外部電源１００の場合は３分ほどの初期期間Ｂｔだけ外部電源１００をカラムヒータ２０に直結する。
　また、設定温度変更期間Ｓｔが経過した後の通常期間Ａｔでは、設定温度指示部３８ａが設定温度をカラム温度に一致させる。設定温度指示部３８ａが設定温度をカラム温度に一致させた後、ＰＩ制御回路４１が行う温度制御は、通常のＰＩ制御になる。 It is not necessary that the set temperature change period St is set from the beginning of the heating of the column heater 20. For example, the initial period Bt corresponds to 60% of the amount of heat necessary to reach the column temperature from the ambient temperature. You may make it give electric energy. In this case, the power supply voltage of the external power supply 100 is applied without performing PWM control. For example, in the case of the 264V external power supply 100, the external power supply 100 is directly connected to the column heater 20 for an initial period Bt of about 1 and a half minutes, and in the case of the 90V external power supply 100, the external power supply 100 is connected to the column heater for an initial period Bt of about 3 minutes. Directly connected to 20.
In the normal period At after the set temperature change period St has elapsed, the set temperature instruction unit 38a matches the set temperature with the column temperature. After the set temperature instruction unit 38a matches the set temperature to the column temperature, the temperature control performed by the PI control circuit 41 is normal PI control.
　実施例においても、電源電圧が９０Ｖであってつまり比較的温度が上がり難い場合でも、３０分以内に分離カラム１５の温度が、測定に必要なカラム温度に安定するように設定されている。しかし、電源電圧が２６４Ｖであってつまり比較的温度が上がり易い場合であっても、図１２に示すように、分離カラム１５の温度がほとんどオーバーシュートしていない。 Also in the embodiment, even when the power supply voltage is 90 V, that is, when the temperature is relatively difficult to rise, the temperature of the separation column 15 is set to be stable to the column temperature necessary for measurement within 30 minutes. However, even when the power supply voltage is 264 V, that is, when the temperature is relatively easy to rise, the temperature of the separation column 15 hardly overshoots as shown in FIG.
　（５）特徴
　（５－１）
　設定温度指示部３８ａは、分離カラム１５の設定温度を指示する。温度測定部である制御サーミスタ３３は分離カラム１５の温度を測定する。温度制御部３７は、設定温度指示部３８ａが指示する設定温度と制御サーミスタ３３が測定した温度との温度差に応じて外部電源１００からカラムヒータ２０に対して出力される電力を制御して分離カラム１５の温度を設定温度に制御する。設定温度指示部３８ａは、カラム温度に達すまでの間の設定温度変更期間では、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更する。
　上記実施例で説明したように、設定温度指示部３８ａが、カラム温度（上記実施形態では３５℃）に達すまでの間の設定温度変更期間Ｓｔでは、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更する。このような制御を行わずに設定温度を一定にした場合には、参考例の図１０に顕著に現れているようにオーバーシュートが発生する。それに対して、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更すると、実施例の図１２に示されているように、オーバーシュートが発生していた期間では、設定温度がカラム温度よりも低くなる。このように、上記期間に設定温度とカラム温度との差分を発生させることで、オーバーシュートを抑制できる。 (5) Features (5-1)
The set temperature instruction unit 38 a instructs the set temperature of the separation column 15. A control thermistor 33 that is a temperature measuring unit measures the temperature of the separation column 15. The temperature control unit 37 controls the power output from the external power source 100 to the column heater 20 according to the temperature difference between the set temperature indicated by the set temperature indicating unit 38a and the temperature measured by the control thermistor 33, thereby separating the separation column. The temperature of 15 is controlled to the set temperature. The set temperature instructing unit 38a changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature changing period until the column temperature is reached.
As described in the above example, in the set temperature change period St until the set temperature instruction unit 38a reaches the column temperature (35 ° C. in the above embodiment), the set temperature is gradually increased to the column temperature as time elapses. Change to get closer. When the set temperature is made constant without performing such control, overshoot occurs as it appears remarkably in FIG. 10 of the reference example. On the other hand, when the set temperature is changed so as to gradually approach the column temperature as time elapses, as shown in FIG. 12 of the embodiment, the set temperature is higher than the column temperature during the period when the overshoot has occurred. Also lower. Thus, overshoot can be suppressed by generating a difference between the set temperature and the column temperature during the period.
　（５－２）
　カラムヒータ２０は、許容電圧範囲の９０Ｖから２６４Ｖまでの中から選択された電源電圧を有する外部電源１００から電力を供給可能に構成されている。そして、温度調節装置３０は、このような電源電圧を有する外部電源１００からカラムヒータ２０に対して出力される電力を制御可能に構成されている。上記実施形態では、許容電圧範囲の中から１００Ｖと２００Ｖを選択した場合の例が説明されている。
　このように、カラムヒータ２０を、許容電圧範囲の９０Ｖから２６４Ｖまでの中から選択された電源電圧を有する外部電源１００から電力を供給可能に構成すると、従来であれば温度調節装置３０の設定が難しい。例えば、オーバーシュートし易い電源電圧に合わせて装置を調整するとオーバーシュートし難い電源電圧でカラム温度に達するのが遅くなり、オーバーシュートし難い電源電圧に合わせて装置を調整するとオーバーシュートし易い電源電圧で大きなオーバーシュートが発生してしまう。それに対して、本実施形態では、設定温度指示部３８ａが、カラム温度に達すまでの間の設定温度変更期間Ｓｔで設定温度を時間経過に従って徐々にカラム温度に近づけるように変更している。したがって、許容電圧範囲の全ての範囲にわたって、カラム温度に達するまでの時間を短縮しながらオーバーシュートを抑制することが容易に行える。 (5-2)
The column heater 20 is configured to be able to supply power from the external power supply 100 having a power supply voltage selected from an allowable voltage range of 90 V to 264 V. And the temperature control apparatus 30 is comprised so that control of the electric power output with respect to the column heater 20 from the external power supply 100 which has such a power supply voltage is possible. In the said embodiment, the example at the time of selecting 100V and 200V from the allowable voltage range is demonstrated.
As described above, if the column heater 20 is configured to be able to supply power from the external power supply 100 having a power supply voltage selected from the allowable voltage range of 90 V to 264 V, setting of the temperature control device 30 is difficult in the prior art. . For example, if the device is adjusted to a power supply voltage that is likely to overshoot, it will slow down to reach the column temperature at a power supply voltage that is difficult to overshoot, and if the device is adjusted to a power supply voltage that is difficult to overshoot, a power supply voltage that is likely to overshoot Will cause a large overshoot. On the other hand, in the present embodiment, the set temperature instructing unit 38a changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature changing period St until the column temperature is reached. Therefore, overshoot can be easily suppressed while reducing the time to reach the column temperature over the entire allowable voltage range.
　（５－３）
　温度調節装置３０は、外部電源１００の電源電圧を検出する電源電圧検出部３６を備えている。温度制御部３７は、電源電圧検出部３６で検出された電源電圧に応じてパルス幅の設定を変更して外部電源１００からカラムヒータ２０に対して出力される電力をＰＷＭ制御するように構成されている。上記実施形態の例では、１６０Ｖよりも低い１００Ｖを電源電圧検出部３６が検出すると、ＰＷＭ信号Ｐ１が出力される期間の最大値（デューティー）が８０ｍｓと長くなる。それに対して、１６０Ｖよりも高い２００Ｖを電源電圧検出部３６が検出すると、ＰＷＭ信号Ｐ２が出力される期間の最大値が２０ｍｓと長くなる。
　その結果、電源電圧が高い場合（２００Ｖ）と低い場合（１００Ｖ）に、カラムヒータ２０に対して供給される電力量を近づけることができ、オーバーシュートのし難い温度制御を行い易くなる。
　なお、上記実施形態では、一つの閾値（上記実施形態では１６０Ｖ）による判別を行って電源電圧が高い場合と低い場合の２通りの変更しか行っていないが、２つ以上の閾値を用いて３通り以上の変更を行ってもよい。また、ＰＷＭ信号が出力される期間の最大値が連続的に変更するように構成されてもよい。 (5-3)
The temperature adjustment device 30 includes a power supply voltage detection unit 36 that detects the power supply voltage of the external power supply 100. The temperature control unit 37 is configured to change the setting of the pulse width according to the power supply voltage detected by the power supply voltage detection unit 36 and to perform PWM control of the power output from the external power supply 100 to the column heater 20. Yes. In the example of the above-described embodiment, when the power supply voltage detection unit 36 detects 100 V lower than 160 V, the maximum value (duty) of the period during which the PWM signal P1 is output becomes as long as 80 ms. On the other hand, when the power supply voltage detection unit 36 detects 200 V higher than 160 V, the maximum value of the period during which the PWM signal P2 is output becomes 20 ms.
As a result, when the power supply voltage is high (200 V) and low (100 V), the amount of power supplied to the column heater 20 can be made close, and temperature control that is difficult to overshoot can be easily performed.
In the above-described embodiment, the determination based on one threshold value (160 V in the above-described embodiment) is performed, and only two kinds of changes are performed, when the power supply voltage is high and when the power supply voltage is low. More changes may be made on the street. Further, the maximum value of the period during which the PWM signal is output may be changed continuously.
　（５－４）
　分離カラム１５は、筒状の樹脂成形品１５ａと、樹脂成形品１５ａの外面を覆う金属被覆１５ｂとを有し、カラムヒータ２０は、金属被覆１５ｂに密接して配設され、金属被覆１５ｂを加熱するように構成されている。これら樹脂成形品１５ａと金属被覆１５ｂとの熱容量が小さいことから、分離カラム１５の温度を早くカラム温度に到達させることができる。その反面、従来であれば、樹脂成形品１５ａと金属被覆１５ｂを用いて構成された分離カラム１５では温度調節時のオーバーシュートが発生しやすくなる。それに対して、本実施形態では、設定温度指示部３８ａが、カラム温度に達すまでの間の設定温度変更期間Ｓｔで設定温度を時間経過に従って徐々にカラム温度に近づけるように変更するので、オーバーシュートを十分に抑制できる。 (5-4)
The separation column 15 has a cylindrical resin molded product 15a and a metal coating 15b covering the outer surface of the resin molded product 15a, and the column heater 20 is disposed in close contact with the metal coating 15b to heat the metal coating 15b. Is configured to do. Since the heat capacities of the resin molded product 15a and the metal coating 15b are small, the temperature of the separation column 15 can be quickly reached the column temperature. On the other hand, conventionally, in the separation column 15 constituted by using the resin molded product 15a and the metal coating 15b, overshoot at the time of temperature adjustment tends to occur. On the other hand, in the present embodiment, the set temperature instructing unit 38a changes the set temperature so as to gradually approach the column temperature as time elapses during the set temperature change period St until the column temperature is reached. Can be sufficiently suppressed.
　（５－５）
　設定温度指示部３８ａは、図１４に示されているような双曲線関数ｆを用いて、設定温度とカラム温度との温度差の変化率が時間経過とともに減少するように設定されていている。このような設定が行われているので、設定温度とカラム温度との温度差の変化率が時間経過によらず一定である場合よりも、さらにオーバーシュートを抑制する効果が高くなっている。 (5-5)
The set temperature instruction unit 38a is set so that the change rate of the temperature difference between the set temperature and the column temperature decreases with time using a hyperbolic function f as shown in FIG. Since such setting is performed, the effect of suppressing the overshoot is higher than when the rate of change of the temperature difference between the set temperature and the column temperature is constant regardless of the passage of time.
　（６）変形例
　以上、本発明の一実施形態について説明したが、本発明は上記実施形態に限定されるものではなく、発明の要旨を逸脱しない範囲で種々の変更が可能である。特に、本明細書に書かれた実施形態及び変形例は必要に応じて任意に組み合せ可能である。
　（６－１）
　上記実施形態では、温度調節装置３０はＰＩ制御回路４１を用いて構成されているが、温度調節装置３０は、他の構成であってもよい。温度調節装置３０は、設定温度指示部が指示する設定温度と温度測定部が測定した温度との温度差に応じて外部電源からカラムヒータに対して出力される電力を制御する他の制御回路で構成されてもよい。例えば、ＰＩ制御回路４１に代えて、比例制御を行う比例制御回路（Ｐ制御回路）を用いてもよい。
　（６－２）
　上記実施形態では、分離カラム１５が筒状の樹脂成形品１５ａとその外面を覆う金属被覆１５ｂとを備えて構成されている場合について説明したが、分離カラム１５の構成はこのようなものに限られるものではない。例えば、筒状の樹脂成形品１５ａとその外面を覆う金属被覆１５ｂの代わりに、筒状のガラス成形品及び／又は筒状の金属成形品を用いることができる。 (6) Modifications One embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment, and various modifications can be made without departing from the scope of the invention. In particular, the embodiments and modifications described in the present specification can be arbitrarily combined as necessary.
(6-1)
In the above embodiment, the temperature adjustment device 30 is configured using the PI control circuit 41, but the temperature adjustment device 30 may have other configurations. The temperature adjusting device 30 is configured by another control circuit that controls the power output from the external power source to the column heater in accordance with the temperature difference between the set temperature indicated by the set temperature indicating unit and the temperature measured by the temperature measuring unit. May be. For example, instead of the PI control circuit 41, a proportional control circuit (P control circuit) that performs proportional control may be used.
(6-2)
In the above embodiment, the case where the separation column 15 is configured to include the cylindrical resin molded product 15a and the metal coating 15b covering the outer surface thereof has been described. However, the configuration of the separation column 15 is not limited to this. It is not something that can be done. For example, instead of the cylindrical resin molded product 15a and the metal coating 15b covering its outer surface, a cylindrical glass molded product and / or a cylindrical metal molded product can be used.
　（６－３）
　上記実施形態では、温度測定部に制御サーミスタ３３を用いる場合について説明したが、温度測定部を構成する部材はサーミスタに限られるものではなく、例えば熱電対、ダイオード、トランジスタ、又はＩＣを用いることができる。また、測定に用いられる温度測定素子である制御サーミスタ３３は１つに限られるものではなく、複数用いることもできる。複数用いた場合には温度測定部が出力する測定値として、例えば平均値又は中央値を用いることもできる。
　（６－４）
　上記実施形態では、設定温度指示部３８ａがＣＰＵ３８によってソフトウェアを用いて形成される場合について説明したが、設定温度指示部３８ａを例えば電子回路のハードウェアで構成してもよい。
　（６－５）
　上記実施形態では、ｆ（λ，ｘ）＝カラム温度＊tanh｛λ＊（ｘ／Ｓｔ）／２｝のように、ｔａｎｈという双曲線関数を用いたが、カラム温度に達すまでの間の設定温度変更期間Ｓｔで、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更するために用いられる関数はこれに限られるものではない。例えば、上述の関数をｘの多項式に展開した関数を用いてもよい。また、上述の関数とは関係の無いｘの多項式を用いて、設定温度を時間経過に従って徐々にカラム温度に近づけるように変更してもよい。 (6-3)
In the above embodiment, the case where the control thermistor 33 is used for the temperature measurement unit has been described. However, the members constituting the temperature measurement unit are not limited to the thermistor, and for example, a thermocouple, a diode, a transistor, or an IC may be used. it can. Further, the control thermistor 33 which is a temperature measuring element used for measurement is not limited to one, and a plurality of thermistors can be used. For example, an average value or a median value can be used as the measurement value output from the temperature measurement unit when a plurality of temperature measurement units are used.
(6-4)
In the above embodiment, the case where the set temperature instruction unit 38a is formed by the CPU 38 using software has been described. However, the set temperature instruction unit 38a may be configured by, for example, hardware of an electronic circuit.
(6-5)
In the above embodiment, a hyperbolic function called tanh is used, such as f (λ, x) = column temperature * tanh {λ * (x / St) / 2}, but the set temperature until the column temperature is reached. The function used for changing the set temperature so as to gradually approach the column temperature as time passes in the change period St is not limited to this. For example, a function obtained by expanding the above function into a polynomial of x may be used. Alternatively, the set temperature may be changed so as to gradually approach the column temperature as time passes by using a polynomial of x that is not related to the above function.
　本発明は、ガスクロマトグラフ及びその温度調節装置並びにガスクロマトグラフの温度調節方法に広く適用できる。 The present invention can be widely applied to a gas chromatograph, its temperature control device, and a gas chromatograph temperature control method.
１０　　　ガスクロマトグラフ
１５　　　分離カラム
１５ａ　　　樹脂成形品
１５ｂ　　　金属被覆
１６　　　半導体ガスセンサ
２０　　　カラムヒータ
３０　　　温度調節装置
３３　　　制御サーミスタ（温度測定部の例）
３６　　　電源電圧検出部
３７　　　温度制御部
３８　　　ＣＰＵ
３８ａ　　　設定温度指示部
１００　　　外部電源 DESCRIPTION OF SYMBOLS 10 Gas chromatograph 15 Separation column 15a Resin molding 15b Metal coating 16 Semiconductor gas sensor 20 Column heater 30 Temperature control apparatus 33 Control thermistor (example of temperature measurement part)
36 Power supply voltage detector 37 Temperature controller 38 CPU
38a Set temperature instruction unit 100 External power supply

Claims (8)

  1. 　キャリアガスにより導入される試料を、所定のカラム温度において複数の成分に分離するための分離カラムと、
    　前記分離カラムを加熱するためのカラムヒータと、
    　前記分離カラムの温度を前記カラム温度に調節するための温度調節装置と、
    を備え、
    　前記温度調節装置は、
    　前記分離カラムの設定温度を指示する設定温度指示部と、
    　前記分離カラムの温度を測定するための温度測定部と、
    　前記設定温度指示部が指示する前記設定温度と前記温度測定部が測定した温度との温度差に応じて外部電源から前記カラムヒータに対して出力される電力を制御して前記分離カラムの温度を前記設定温度に制御する温度制御部と、
    を含み、
    　前記設定温度指示部は、前記カラム温度に達すまでの間の設定温度変更期間では、前記設定温度を時間経過に従って徐々に前記カラム温度に近づけるように変更する、ガスクロマトグラフ。     A separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature;
    A column heater for heating the separation column;
    A temperature adjusting device for adjusting the temperature of the separation column to the column temperature;
    With
    The temperature control device is:
    A set temperature indicating unit for indicating the set temperature of the separation column;
    A temperature measuring unit for measuring the temperature of the separation column;
    The temperature of the separation column is controlled by controlling the power output from the external power source to the column heater according to the temperature difference between the set temperature indicated by the set temperature indicating unit and the temperature measured by the temperature measuring unit. A temperature control unit for controlling the set temperature;
    Including
    The gas temperature chromatograph, wherein the set temperature instruction unit changes the set temperature so as to gradually approach the column temperature as time elapses during a set temperature change period until the column temperature is reached.
  2. 　前記カラムヒータは、所定の許容電圧範囲から選択された電源電圧を有する前記外部電源から電力を供給可能に構成され、
    　前記温度調節装置は、当該電源電圧を有する前記外部電源から前記カラムヒータに対して出力される電力を制御可能に構成されている、
    請求項１に記載のガスクロマトグラフ。     The column heater is configured to be able to supply power from the external power supply having a power supply voltage selected from a predetermined allowable voltage range,
    The temperature adjusting device is configured to be able to control electric power output to the column heater from the external power supply having the power supply voltage.
    The gas chromatograph according to claim 1.
  3. 　前記外部電源の前記電源電圧を検出する電源電圧検出部をさらに備え、
    　前記温度制御部は、前記電源電圧検出部で検出された前記電源電圧に応じてパルス幅の設定を変更して前記外部電源から前記カラムヒータに対して出力される電力をＰＷＭ制御する、
    請求項２に記載のガスクロマトグラフ。     A power supply voltage detection unit for detecting the power supply voltage of the external power supply;
    The temperature control unit changes the setting of the pulse width according to the power supply voltage detected by the power supply voltage detection unit, and performs PWM control of the power output from the external power supply to the column heater,
    The gas chromatograph according to claim 2.
  4. 　前記分離カラムは、筒状の樹脂成形品と、前記樹脂成形品の外面を覆う金属被覆とを有し、
    　前記カラムヒータは、前記金属被覆に密接して配設され、前記金属被覆を加熱する、
    請求項１から請求項３のいずれか一項に記載のガスクロマトグラフ。     The separation column has a cylindrical resin molded product and a metal coating covering an outer surface of the resin molded product,
    The column heater is disposed in close contact with the metal coating to heat the metal coating;
    The gas chromatograph according to any one of claims 1 to 3.
  5. 　前記設定温度指示部は、前記設定温度と前記カラム温度との温度差の変化率が時間経過とともに減少するように設定されている、
    請求項１から請求項４のいずれか一項に記載のガスクロマトグラフ。     The set temperature instruction unit is set so that the rate of change of the temperature difference between the set temperature and the column temperature decreases with time.
    The gas chromatograph according to any one of claims 1 to 4.
  6. 　キャリアガスにより導入される試料を、所定のカラム温度において複数の成分に分離するための分離カラムと前記分離カラムを加熱するためのカラムヒータとを備えるガスクロマトグラフの前記分離カラムの温度を前記カラム温度に調節するための温度調節装置であって、
    　前記分離カラムの設定温度を指示する設定温度指示部と、
    　前記分離カラムの温度を測定するための温度測定部と、
    　前記設定温度指示部が指示する前記設定温度と前記温度測定部が測定した温度との温度差に応じて外部電源から前記カラムヒータに対して出力される電力を制御して前記分離カラムの温度を前記設定温度に制御する温度制御部と、
    を含み、
    　前記設定温度指示部は、前記カラム温度に達すまでの間の設定温度変更期間では、前記設定温度を時間経過に従って徐々に前記カラム温度に近づけるように変更する、ガスクロマトグラフの温度調節装置。     A temperature of the separation column of a gas chromatograph including a separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature and a column heater for heating the separation column is set to the column temperature. A temperature control device for adjusting,
    A set temperature indicating unit for indicating the set temperature of the separation column;
    A temperature measuring unit for measuring the temperature of the separation column;
    The temperature of the separation column is controlled by controlling the power output from the external power source to the column heater according to the temperature difference between the set temperature indicated by the set temperature indicating unit and the temperature measured by the temperature measuring unit. A temperature control unit for controlling the set temperature;
    Including
    The temperature adjustment device for a gas chromatograph, wherein the set temperature instruction unit changes the set temperature so as to gradually approach the column temperature as time elapses during a set temperature change period until the column temperature is reached.
  7. 　前記カラムヒータは、所定の許容電圧範囲から選択された電源電圧を有する前記外部電源から電力を供給可能に構成され、
    　前記温度制御部は、前記外部電源の前記電源電圧を検出する電源電圧検出部を含み、前記電源電圧に応じてパルス幅の設定を変更して前記外部電源から前記カラムヒータに対して出力される電力をＰＷＭ制御する、
    請求項６に記載のガスクロマトグラフの温度調節装置。     The column heater is configured to be able to supply power from the external power supply having a power supply voltage selected from a predetermined allowable voltage range,
    The temperature control unit includes a power supply voltage detection unit that detects the power supply voltage of the external power supply, and changes the setting of the pulse width according to the power supply voltage and is output from the external power supply to the column heater PWM control,
    The temperature control apparatus of the gas chromatograph of Claim 6.
  8. 　キャリアガスにより導入される試料を、所定のカラム温度において複数の成分に分離するための分離カラムと前記分離カラムを加熱するためのカラムヒータとを備えるガスクロマトグラフの前記分離カラムの温度を前記カラム温度に調節する温度調節方法であって、
    　前記分離カラムの設定温度を指示する設定温度指示ステップと、
    　前記分離カラムの温度を測定する温度測定ステップと、
    　前記設定温度指示ステップで指示された前記設定温度と前記温度測定ステップで測定された温度との温度差に応じて外部電源から前記カラムヒータに対して出力される電力を制御して前記分離カラムの温度を前記設定温度に制御する温度制御ステップと、
    を含み、
    　前記設定温度指示ステップでは、前記カラム温度に達すまでの間の設定温度変更期間では、前記設定温度が時間経過に従って徐々に前記カラム温度に近づくように変更される、
    ガスクロマトグラフの温度調節方法。     A temperature of the separation column of a gas chromatograph including a separation column for separating a sample introduced by a carrier gas into a plurality of components at a predetermined column temperature and a column heater for heating the separation column is set to the column temperature. A temperature control method for adjusting,
    A set temperature indicating step for indicating a set temperature of the separation column;
    A temperature measuring step for measuring the temperature of the separation column;
    The temperature of the separation column is controlled by controlling the power output from the external power source to the column heater according to the temperature difference between the set temperature instructed in the set temperature instructing step and the temperature measured in the temperature measuring step. A temperature control step for controlling the temperature to the set temperature;
    Including
    In the set temperature instruction step, in the set temperature change period until the column temperature is reached, the set temperature is changed so as to gradually approach the column temperature as time elapses.
    Gas chromatograph temperature control method.
PCT/JP2016/063327 2015-05-13 2016-04-28 Gas chromatograph, temperature controller for same, and gas chromatograph temperature control method WO2016181853A1 (en)

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