KR20040012068A - Gaseous sample injection apparatus for gaschromatography - Google Patents

Abstract

PURPOSE: Provided is an injector for the analysis of volatile organic compounds present in air, soil, or water which is highly efficient in thermodesorption and is possible to conduct fast analysis using a small amount of sample, thus it is applicable to fast Gas Chromatography(GC), because the desorption is conducted under a reduced vacuum condition and the concentration of desorbed sample is very high. CONSTITUTION: The injector for the analysis of volatile organic compounds comprises: a dryer(70) in which samples taken from air, water or soil are dried by the drying air reserved in an air storage tank(10); a separating column(20) which absorbs samples at a low temperature and desorbs samples at an elevated temperature, in which the dried samples are absorbed by condensation at low temperature or desorbed by heating; a sample-collecting pump(29) introducing samples taken from air, water or soil into the dryer(70) and also the dried samples from the dryer(70) to the separating column(20); a sample storage and supplying device(43) in which the desorbed sample from the separating column(20) is aspirated for storage under a reduced pressure, then the stored samples are discharged; a first control valve(30) which controls the route of the samples from the dryer(70) to the separating column(20), from the air storage tank(10) to the separating column(20), or from the separating column(20) to the sample storage and supplying device(43); a vacuum control valve(26) which controls the supply of the drying air passed through the first control valve(30) to the separating column(20); a sampling loop(51) in which samples discharged from the sample storage and supplying device(43) are sampled to a certain concentration; a secondary control valve(40) which controls the route of the desorbed samples passed through the first control valve(30) to the sample storage and supplying device(43) or the route of the samples discharged from the device (43) to the sampling loop(51); a secondary vacuum control valve(42) located between the secondary control valve(40) and the device(43) to control the route of the samples; a carrier-gas storage tank(60) for carrying the samples from the sampling loop(51); and a third control valve(50) which controls the route of samples from the secondary control valve(40) to sample loop(51), or samples from the sampling loop(51) to an analysis device(90).

Description

Sample injection device of volatile organic compound analyzer {GASEOUS SAMPLE INJECTION APPARATUS FOR GASCHROMATOGRAPHY}

The present invention relates to a sample injection device used in a volatile organic compound analysis device, in particular to collect a volatile organic compound, such as fast gas chromatography (hereinafter, abbreviated as 'Fast GC') to be analyzed in a short time A sample injection device used in the device.

Gas chromatography (Gas Chromatography, hereinafter abbreviated as 'GC') is commonly used to analyze volatile organic compounds. In order to inject the sample into the GC, due to the strong volatility of the sample, the liquid liquefaction sample injection method using the liquid nitrogen or liquid argon liquefied and then injected, and the gas sample collected in the solid adsorption tube without liquefied concentration of the gas sample There is a thermal desorption method that directly injects GC while applying heat to the adsorption tube.

The liquefied concentrated sample injection method is uneconomical because it requires expensive liquefied concentrated equipment, and the conventional thermal desorption method is capable of desorption of the sample with respect to the heating time, no matter how quickly the adsorption tube is heated in the process of heating and desorbing the sample in the adsorption tube. Inconsistent tailing (tailing) occurs, which results in a problem that the detection limit is lowered due to the overlap (overlap) phenomenon that the samples overlap each other in the GC. In addition, there is a risk that the temperature unstable compounds are damaged in the pre-separation step due to the rapid temperature increase during the desorption process.

In addition, in the thermal desorption method, the amount of adsorbent may be increased so as to adsorb a sufficient sample in the sample adsorption step before thermal desorption so that a sufficient amount of sample is desorbed during thermal desorption, but when the amount of the adsorbent is increased, the carrier gas necessary for desorption of the sample ( Since the amount of carrier gas increases, the sample dilution rate increases, and thus, there is a limit to increasing the amount of carrier gas to maintain the concentration of the sample above a certain level. In addition, the sample injection time injected into the analyzer by a large amount of carrier gas becomes long, and there is a problem in that a narrow inner diameter separation tube cannot be used.

When the sample analysis time is forcibly shortened due to the above problems, separation of the analyte is not normally performed in the sample analysis device, thereby reducing the accuracy of the analysis. Therefore, when the volatile organic compounds are analyzed by the above method, the analysis time is shorter to 30 to 40 minutes and longer to 60 minutes or longer. Fast GC assays are generally limited to the analysis of about 10 specific substances and there are limits to the application of Fast GC assays for more than 50 regulated contaminants. In addition, the use of these Fast GC methods generally requires many additional expensive equipment. The most commonly used equipment is a sensitive mass spectrometer, a high performance heating oven for sample analysis, and capillary separation of samples under high pressure. There is an injection device that can be injected into the tube.

In general, the resolution of GC capillary tube is related to the inner diameter of capillary tube. If the inner diameter is reduced twice, the resolution will be the same even if the length of the entire separator is reduced twice. At the same time, there is a significant reduction in analysis time. However, when the inner diameter is reduced, the sample injection capacity is reduced, making it impossible to use for an analysis requiring high sensitivity. Applications such as chemistry, petrochemicals, food, taste and fragrance analysis do not require high sensitivity, but in areas requiring high sensitivity such as environmental analysis, it is difficult to shorten the analysis time unless high concentration samples are injected. have.

Therefore, the present invention is designed to solve the problems of the conventional sample injection device that was not applicable to Fast GC as described above, while analyzing the sample concentrated in a certain amount of high concentration within a short time while preventing the sample dilution by the sample carrier gas The objective is to provide a sample injection device capable of fast GC analysis by injection into the device.

The sample injection device of the volatile organic compound analysis device of the present invention for achieving the above object is a sample dryer for drying the volatile organic compound sample taken from the air, water source or soil with a dry body stored in a gas storage tank for drying and washing, A low temperature adsorption heat desorption separation tube for concentrated adsorption at low temperature or the heating and desorption of the sample dried in the sample dryer, and a volatile organic compound sample generated in the air, a water source, or the soil are introduced into a sample dryer, and dried in a sample dryer. A sample collection pump for introducing a sample into a low temperature adsorption thermal desorption separation tube, a sample storage / supply apparatus for suction-storing the sample desorbed and discharged from the low temperature adsorption thermal desorption separation tube under a reduced pressure vacuum, and pressurizing and discharging the stored sample; Supply or block the sample from the sample dryer to the low temperature adsorption heat desorption separation tube (B) a first control valve for supplying or blocking the cleaning gas from the drying / cleaning gas storage tank to the low temperature adsorption thermal desorption separation tube or for supplying or blocking the desorbed sample from the low temperature adsorption thermal desorption separation tube to the sample storage / supply device; The first vacuum control valve for supplying or blocking the cleaning gas passing through the first control valve to the low temperature adsorption heat desorption separation tube and the sample discharged from the sample storage / supply device are passed through the roofing tube to uniform the concentration. A sample loop for concentrating and sampling the sample loop and a desorbed sample discharged through the first control valve to the sample storage supply device or to the sample loop supplying the sample discharged from the sample storage supply device toward the sample loop. Connected to the second control valve and the sample storage supply device to supply or cut off the sample; Supply a second vacuum control valve, a carrier gas storage tank for storing a carrier gas for transporting the sampled sample of the sample loop to the sample analysis device, and supplies the sample discharged through the second control valve to the sample loop or Or a third control valve for blocking or supplying or blocking the sample in the sample loop to the sample analyzer.

The sample injection device according to the present invention does not receive pressure from the carrier gas when the sample is thermally desorbed from the adsorption agent of the low temperature adsorption thermal desorption separation tube and there is no supply of additional gas, so that a high concentration of the sample can be obtained and always through the sample loop. Since a small amount of high concentration sample is supplied to the sample analyzer for a short time, not only can the tailing phenomenon of the sample dropping in the GC analysis column be improved, but also the reproducibility can be greatly improved. A small amount can be injected and at the same time a fast sample injection time can be obtained, and a small amount of sample injected into the analytical capillary separation tube enables the use of a narrow inner diameter (100-200 μm) separation tube.

1 is a configuration diagram schematically showing the configuration of a sample injection device of the volatile organic compound analysis device according to the present invention,

Figure 2a is a schematic diagram showing a state in which the control valve of the present invention operates in the sample collection step, the sample drying step and the sample low temperature adsorption step,

Figure 2b is a schematic diagram showing a state in which the control valve of the present invention operating in the sample removal step and the sample storage step,

Figure 2c is a schematic view showing a state in which the control valve of the present invention operating in the low temperature adsorption heat desorption separation tube washing step,

Figure 2d is a schematic diagram showing a state in which the control valve of the present invention operating in the sample sampling step,

Figure 2e is a schematic diagram showing a state in which the control valve of the present invention operating in the sample injection step,

Figure 3 is a graph of the analysis results of analyzing the standard material of volatile organic compounds using a sample injection device of the volatile organic compound analysis device according to the present invention.

※ Explanation of code for main part of drawing

10: gas storage tank for washing and drying 20: low temperature adsorption heat desorption separation tube

21: first connection line 22: first variable flow control valve

23: second connection line 24: second variable flow control valve

25: third connection line 26: first vacuum control valve

27: fourth connection line 28: sample flow rate control valve

29: Sampling Pump 30: First Control Valve

31: fifth connection line 33: sixth connection line

40: second control valve

41: 7th connection line 42: second vacuum control valve

43: sample storage and supply device 44: eighth connection line

50: third control valve 51: sample loop (sample loop)

52: ninth connection line 53: third variable flow control valve

54: tenth connection line 55: flow restrictor

56: heating oven for sample analysis

60: carrier gas storage tank 70: sample drying device

80: capillary separation tube 90: sample analysis device

Hereinafter, embodiments according to the present invention will be described in detail according to the accompanying drawings.

Figure 1 is a schematic diagram showing the configuration of a sample injection device of the volatile organic compound analysis device according to the present invention.

As shown in FIG. 1, the present invention includes a sample dryer 70 for drying a sample of volatile organic compounds collected in air, water, or soil, and collects a predetermined amount of the sample dried in the sample dryer 70. Adsorption thermal desorption separation tube 20, the cold adsorption thermal desorption separation tube 20 and the sample dryer 70 is in communication with each other through the third, fourth connection lines (25, 27).

In addition, the present invention includes a washing and drying gas storage tank 10 for storing the gas used to wash the low temperature adsorption heat desorption separation tube 20 or to dry the sample introduced into the sample dryer 70.

As the sample dryer 70, a so-called Nafion Drier is commonly used, and the sample dryer 70 is in communication with the gas storage tank 10 for cleaning and drying through the first connection line 21. have. Helium or nitrogen gas is usually used as a drier flowing into the sample drier 70 from the gas storage tank 10 for washing and drying, and the drier passes through the sample drier 70 and is discharged to the outside. The sample is contacted with the sample introduced into the dryer 70 to dry the sample.

The low temperature adsorption heat desorption separation tube (20) is filled with an adsorbent therein, and a cold plate and a heating wire whose operation is controlled by a cooling and heating temperature control device are wound around the low temperature adsorption heat desorption separation tube (20). Cooling or heating. The adsorbents used in the low temperature adsorption thermal desorption separation tube 20 can be selected and used by the analyst according to the material to be analyzed.

The present invention includes a sample collecting pump 29 necessary for collecting a sample, wherein the sample collecting pump 29 communicates with the low temperature adsorption heat desorption separation tube 20 and the sixth connection line 33. The sample flow rate control valve 28 is provided on the sixth connection line 33 to adjust the amount of the sample introduced into the sample dryer 70 and the low temperature adsorption thermal desorption separation tube 20.

The sample to be analyzed is introduced into the sample dryer 70 through the fourth connection line 27 from the outside by the sample collecting pump 29 and dried, and the dried sample is collected by the sample collecting pump 29. Passed through the fourth connection line 27 and the third connection line 25 is concentrated adsorption to the adsorbent while being introduced into the low temperature adsorption heat desorption separation tube 20 cooled by about 30 ° C by the cooling temperature control device.

After enough samples are adsorbed to the low temperature adsorption thermal desorption separation tube (20), the power supply is applied to the heating wire surrounding the low temperature adsorption thermal desorption separation tube (20) while maintaining the operation of the cold plate. The sample adsorbed on the adsorbent is thermally desorbed by heating. At this time, the heating temperature of the low temperature adsorption thermal desorption separation tube 20 varies depending on the sample type, but is about 200 to 350 ° C.

Since the adsorbent of the low temperature adsorption heat desorption separation tube (20) collects a sample at a low temperature, not at room temperature, the adsorbent has an advantage of using less than 1/5 of the amount of the adsorbent used in a general heat desorption apparatus. The amount of 하게 makes the vacuum desorption of the sample in the low temperature adsorption thermal desorption separation tube 20 very efficient, and serves as a basic role of transferring a high concentration of sample to the sample loop 51 to be described later.

On the other hand, the first variable flow rate control valve 22 is installed on the first connection line 21 to adjust the amount of gas supplied from the gas storage tank 10 for washing and drying to the sample dryer 70. The second variable flow control valve 24 is installed on the second connection line 23 to adjust the amount of gas supplied from the gas storage tank 10 for washing and drying to the low temperature adsorption thermal desorption separation tube 20. Can be. This is to adjust the amount of gas required for washing the low temperature adsorption heat desorption separation tube 20 according to the type of sample and the amount of supply of the dry gas according to the type of sample, and to control the speed of each gas.

The first vacuum control valve 26 is connected to one side of the third connection line 25 connected to the low temperature adsorption thermal desorption separation tube 20, and the first control valve 30 is connected to the other side. 30 and the second control valve 40 are connected via the fifth connection line 31, the second control valve 40 and the second vacuum control valve 42 is connected to the seventh connection line (41). The second vacuum control valve 42 and the sample storage / supply device 43 are connected by a seventh connection line 41.

The first vacuum control valve 26 is opened during the sample collection process of the low temperature adsorption thermal desorption separation tube 20, and the sample dried in the sample dryer 70 is operated by the collection pump 29. ), And the desorption process is blocked in the thermal desorption process to create a vacuum pressure so that the sample adsorbed on the adsorbent is efficiently desorption, wherein the second vacuum control valve 42 is opened so that the desorbed sample is the first control valve (30) After the fifth connection line 31 and the second control valve 40, the suction and storage to the sample storage and supply device 43, the second vacuum control valve 42 is cut off again after a certain time The sample stored in the storage / supply device 43 serves to maintain the same as the external air pressure.

When the thermal desorption of the sample is completed as described above, the first vacuum control valve 26 is opened again so that the washing dryer flows into the low temperature adsorption heat desorption separation tube 20 to clean the low temperature adsorption heat desorption separation tube 20. And this series of processes is possible by the operation of the first control valve 30 and the second control valve 40.

The sample storage / supply device 43 sucks and stores a sample which is thermally desorbed and discharged from the low temperature adsorption heat desorption separation tube 20 by an inhaler under a reduced pressure vacuum, and is stored toward a sample loop 51 for sampling a predetermined amount of sample It serves to pressurize and discharge the sample. In this case, a heating device for applying heat to the sample storage / supply device 43 may be provided to activate the sample stored in the sample storage / supply device 43 to uniformize the density before pressurizing the sample. As the heating device, a heater blower or a heating wire is used.

The second control valve 40 is connected to the third control valve 50 and the eighth connection line 44 to control the sample sample stored in the sample loop 51. Therefore, the sample stored in the sample storage / supply device 43 is sampled through the second vacuum control valve 42, the second control valve 40, the eighth connection line 44, and the third control valve 50. Is sent to loop 51.

The sample loop 51 is formed of a spiral tube of a predetermined volume, so that the sample flow in the sample loop 51 is smaller than the straight tube, so that the sample will remain in the tube without being discharged unless it is pressurized from the rear, so that a certain amount of sample is accommodated. It plays a role. However, if there is an abnormal increase or abnormality in the external pressure, the internal volume of the sample loop 51 may be small, so that an error in the analysis result may occur. The flow restrictor 55 may be installed to minimize the influence of the change in external pressure.

The third control valve 50 selectively connects the carrier gas storage tank 60 and the sample loop 51 to each other. The third control valve 50 connects the third control valve 50 and the carrier gas storage tank 60 to each other. The third variable flow rate control valve 53 is installed on the ninth connection line 52 to adjust the amount of carrier gas. When the carrier gas is supplied from the carrier gas storage tank 60 toward the sample loop 51, the carrier gas samples a certain amount of sample contained in the sample loop 51 through the tenth connection line 54. The sample carrier gas is mainly used in an inert gas such as helium or nitrogen so as not to react with the sample.

In addition, on the tenth connection line 54, a sample analysis heating oven 56 including a capillary separation tube 80 is installed to adjust the temperature of the capillary separation tube according to the sample analysis conditions, and separate the sample by component. do.

The first control valve 30, the second control valve 40, and the third control valve 50 preferably use a six-port rotary valve.

Hereinafter, the operation of the sample injection device of the present invention will be described in detail step by step from Figure 2a to Figure 2e.

Sample collection step;

Figure 2a is a schematic diagram showing a state in which the control valve of the present invention operates in the sample collection step, the sample drying step and the sample low temperature adsorption step.

When the sample injection device of the present invention is installed in the source or region of the desired sample to be analyzed, and a predetermined amount of air controlled by the sample flow control valve 28 for a predetermined time is sucked by using the sample collection pump 29 The volatile organic compounds or the volatile organic compounds in the air discharged from the soil or the river are sucked into the sample dryer 70 through the fourth connection line 27, and passed through the sample dryer 70 to form a low temperature adsorption heat desorption separator tube ( 20) is collected and collected.

Sample drying step;

When the first variable flow rate control valve 22 installed in the first connection line 21 is opened, the sample drying gas stored in the cleaning / drying gas storage tank 10 is sampled through the first connection line 21. The sample 70 is introduced into the dryer 70 to dry the sample while contacting the sample inside the sample dryer 70. At this time, the flow rate of the dry matter passing through the first variable flow rate control valve 22 is generally 100 ml / min, but is adjustable according to the amount of water in the sample and the analyte.

Sample low temperature adsorption step;

The dried sample is introduced into the low temperature adsorption thermal desorption separation tube 20 maintained at a low temperature of about -30 ° C. by the cooling device of the low temperature adsorption thermal desorption separation tube 20 and adsorbed to the adsorbent.

Sample desorption step;

Figure 2b is a schematic diagram showing a state in which the control valve of the present invention operates in the sample removal step and the sample storage step.

The low temperature adsorption thermal desorption separation tube 20 in which the sample is collected is heated by a heating apparatus. At this time, the first vacuum control valve 26 is in a state of blocking the flow of air, the temperature for heating the low temperature adsorption heat desorption separation tube 20 is slightly different depending on the type of sample, but is about 200 ~ 350 ℃. As such, when the low temperature adsorption thermal desorption separation tube 20 is heated, the sample collected therein is desorbed while evaporating.

Sample storage step;

The removed sample is moved to the sample storage / supply device 43 through the first control valve 30, the second control valve 40, and the second vacuum control valve 42 through the third connection line 25. do. At this time, the vacuum pressure is made of a glass inhaler used as the sample storage and supply device 43 is drawn, the degree of vacuum is also changed depending on the amount of the pulled. When the desorption is completed, the second vacuum control valve 42 blocks the flow of air to prevent the sample inside the sample storage / supply device 43 from being diluted and contaminated by external air, and compresses the glass inhaler again and again. Maintain internal pressure equal to external air pressure.

Low temperature adsorption heat desorption separation tube washing step;

Figure 2c is a schematic diagram showing a state in which the control valve of the present invention operates in the low temperature adsorption heat desorption separation tube washing step.

Passing the cleaning and drying gas through the low temperature adsorption heat desorption separation tube (20) where the heat desorption is completed, the first vacuum control valve (26) maintains the flow of air again by washing the sample remaining therein. The gas for washing and drying, whose flow rate is controlled by the second variable flow control valve 24, passes through the first vacuum control valve 26 through the first control valve 30, and then is a low temperature adsorption thermal desorption separation tube in a high temperature state. While passing through 20, the sample remaining inside is washed, and the cleaning gas flows out through the first control valve 30 to the second control valve 40.

Sample sampling step;

Figure 2d is a schematic diagram showing a state in which the control valve of the present invention operates in the sample sampling step.

Samples collected in the sample storage / supply device 43 are heated and activated by adjacently arranged heating devices, and at the same time, the distribution density is uniform. Then, as shown in FIG. 2D, the second control valve 40 is switched to connect the sample storage / supply device 43 and the third control valve 50, and the position of the third control valve 50 is When the second control valve 40 and the sample loop 51 are switched to be connected, the second vacuum control valve 42 is opened to maintain the flow of air, and is used as the sample storage / supply device 43. The glass inhaler is compressed to push the sample into the sample loop 51.

Sample injection step;

Figure 2e is a schematic diagram showing a state in which the control valve of the present invention operates in the sample injection step.

When the sample is to be stored in the sample loop 51, the third control valve 50 is switched so that the carrier gas storage tank 60 and the sample loop 51 are connected to the sample loop 51 by the sample carrier gas. The internal sample is to be delivered to the capillary separation tube 80 inside the heating oven 56 for sample analysis. In this process, a high concentration of a small amount of sample is sent to the sample analyzer in a short time. In addition, the sample analyzer is able to use a capillary tube with a narrow inner diameter because a small amount of sample is injected, thereby reducing the analysis time.

The sample collection, low temperature adsorption and vacuum desorption and the sample storage, dispensing and injection step can be automatically controlled by the control computer, respectively. Therefore, it has many advantages in terms of efficient and productive workforce.

Figure 3 is an example of analysis using a sample injection device of the volatile organic compound analysis device according to the present invention is a graph of the analysis results of direct analysis of the standard material of volatile organic compounds that are regulated by the US Environmental Protection Agency (EPA). (GC: DS6200, Detector: Flame Ionization Detector, Capillary Separator: SPB-1 Length-10m Inner Diameter-0.2mm).

As shown in FIG. 3, the components of the volatile organic compounds can be efficiently analyzed even with a 10 m capillary separation tube, and analysis is performed in comparison with the conventional GC analysis time, which takes 30 to 60 minutes or more after completing the analysis within 8 minutes. It can be seen that the time is very short.

In the present invention, since the sample is adsorbed at a low temperature, it is possible to use a smaller amount of the adsorbent than the conventional sample injection device, and the thermal desorption efficiency is very high because the sample is thermally desorption under vacuum, and the capacity of the desorbed high concentration sample is very high. A small sample loop always injects a small amount into the sample analyzer for a very short time, allowing the use of a narrow inner diameter into the GC's capillary column, enabling the Fast GC method.

In addition, the present invention can be analyzed by the use of a separation tube of 10m or less, compared to the conventional sample injection device used in GC having an analytical capillary separation tube of 30 to 60m, it is possible to inject a high concentration sample In general, the detector can be easily used as a detector, and the amount of gases consumed is reduced due to the reduction of analysis time, thereby reducing the overall cost.

In addition, the present invention can be used as an existing analytical equipment without using liquid nitrogen and expensive detectors, so it is possible to obtain additional cost reduction due to the change of equipment, and also to reduce the operation and material costs of using the existing equipment. Can bring In addition, the present invention uses a valve system and a sample loop having a simple structure and operation principle, and thus is convenient to automate, thereby reducing a lot of manpower and improving reliability of an analysis result due to analysis automation. In addition, many different types of analytes can be analyzed in a short time. As it becomes possible to use Fast GC that can specifically inform the causative agent of hazardous environment, it is possible to respond quickly to harmful environment and protect health and the environment.

Claims (5)

A sample dryer 70 for drying a volatile organic compound sample collected from the air, a water source, or soil with a dry gas stored in a drying / washing gas storage tank 10; A low temperature adsorption heat desorption separation tube (20) for concentrated adsorption or drying by heating the sample dried in the sample dryer (70); Sample collection pump (29) for introducing the volatile organic compound sample generated in the atmosphere, water or soil into the sample dryer (70), and the sample dried in the sample dryer (70) into the low temperature adsorption heat desorption separation tube (20). ); A sample storage / supply device 43 which sucks and stores a sample which is detached and discharged from the low temperature adsorption heat desorption separation tube 20 in a vacuum under reduced pressure, and pressurizes and discharges the stored sample; Supply or block the sample from the sample dryer 70 to the low temperature adsorption heat desorption separation tube 20, or supply or block the cleaning gas from the drying / cleaning gas storage tank 10 toward the low temperature adsorption heat desorption separation tube 20. Or a first control valve 30 for supplying or blocking a sample desorbed from the low temperature adsorption thermal desorption separation tube 20 toward the sample storage / supply device 43; A first vacuum control valve 26 for supplying or blocking the cleaning gas passing through the first control valve 30 to the low temperature adsorption thermal desorption separation tube 20; A sample loop 51 for uniformly concentrating and sampling a sample discharged from the sample storage and supply device 43; The desorbed sample discharged through the first control valve 30 is supplied or blocked to the sample storage / supply device 43, or the sample pressurized and discharged from the sample storage supply device 43 is toward the sample loop 51. A second control valve 40 to supply or shut off; A second vacuum control valve 42 connected to the second control valve 40 and the sample storage supply device 43 to supply or block a sample; A carrier gas storage tank (60) for storing a carrier gas for transporting the sampled sample of the sample loop (51) to a sample analyzer (90); A third control valve for supplying or blocking the sample discharged through the second control valve 40 to the sample loop 51 or for supplying or blocking the sample of the sample loop 51 to the sample analyzer 90 ( 50); Sample injection device of volatile organic compound analysis device comprising a. The sample for controlling the amount of the sample introduced into the sample dryer (70) on the sixth connection line (33) for communicating the sample collection pump (29) and the low temperature adsorption thermal desorption separation tube (20) with each other. Flow rate control valve 28 is installed, the drying gas flowing into the sample dryer 70 on the first connection line 21 for communicating the drying and washing gas storage device 10 and the sample dryer 70 with each other. A first variable flow rate control valve 22 for adjusting the flow rate of the gas is provided, and on the second connection line 23 for communicating the drying / washing gas storage device 10 and the first control valve 30 with each other, A second variable flow rate control valve 24 for adjusting the flow rate of the cleaning gas flowing into the first control valve 30 is installed, and the carrier gas storage tank 60 and the third control valve 50 communicate with each other. Third variable for adjusting the flow rate of the carrier gas flowing into the third control valve 50 on the ninth connection line 52 Sample injection device of the volatile organic compound analysis device, characterized in that the flow control valve 53 is installed. The sample analyzing apparatus according to claim 1 or 2, wherein the sampled sample discharged through the third control valve is selectively heated while passing through the capillary separation tube (80) to concentrate a small amount of sample to the sample analyzing apparatus (90). Sample injection device of the volatile organic compound analysis device, characterized in that it further comprises a heating oven (56) for outgoing sample analysis. The sample injection device according to claim 1 or 2, wherein the sample storage and supply device (43) further comprises a heating device for heating and activating a sample stored therein. The method of claim 1 or 2, further comprising a flow restrictor (55) connected to the third control valve (50) for adjusting the internal pressure of the sample loop (51). Sample injection device of volatile organic compound analysis device.