KR20110092936A - Apparatus for analyzing samples with ultralow temperature concentration modules - Google Patents

Abstract

PURPOSE: A sample analysis apparatus is provided to analyze the concentration of each diluted reference gas obtained by mixing reference gas and dilute gas in various mixture ratios. CONSTITUTION: A sample analysis apparatus(1) includes a super low temperature concentrating system and a diluting device(50) supplying reference gas after diluting. The diluting device includes the following a reference gas supply line(51) and a diluted gas supply line(53); a flow speed controller(42) controlling the flowing amount and speed of each gas; a mixing chamber(56) for mixing the reference gas and diluted gas; and a heating block(55) for heating each gas flowing into the mixing chamber.

Description

Apparatus for analyzing samples with ultralow temperature concentration modules

The present invention relates to a sample analysis device, and more specifically, it is possible to analyze at various concentrations through various dilution multiples by constructing a dilution device for quantitative analysis, and to analyze a sample using a cryogenic concentration system which improves the adsorption performance of the sample. Relates to a device.

Currently, gas chromatography (Gas Chromatography, hereinafter abbreviated as 'GC') is used to analyze volatile organic compounds.The sample is collected by injecting a certain amount of the sample into the GC. In the case of the sample, since the sample is highly volatile, the liquefied concentrated sample injection method in which the sample is liquefied and concentrated by using inert liquid nitrogen or liquid argon, and the gas sample is collected in the solid adsorption tube without liquefied concentration and then adsorbed. A so-called thermal desorption method is used in which the tube is directly injected into the GC while heating the tube. However, the liquefied concentrated sample injection method is disadvantageous because it requires an expensive liquefied concentrated equipment, the thermal desorption method is commonly used in VOC analysis. The VOC sample to be analyzed is adsorbed to the adsorption tube by a suction pump, and once collected, the collected VOC sample is desorbed while being heated to a high temperature and transferred to an analytical device such as GC.

In particular, such an online unmanned system is to check periodically by linking the standard gas for quantitative analysis. Existing systems are designed to pre-link a gas produced at one concentration and replace it after a period of use.

However, these standard gases are mostly imported, not only very expensive, but also quickly consumed due to their small capacity, which often leads to a decrease in productivity and waste of manpower and time by frequently replacing adsorbents and standard gases in online unmanned systems. Rather, it is difficult to ensure economic problems and the accuracy of the analysis.

In addition, before the sample is injected into the GC for quantitative analysis, it is adsorbed in the adsorption tube and concentrated to a low temperature of about -10 ° C to -30 ° C, wherein some of the samples have low boiling point samples having a boiling point of -70 ° C or lower. Since the low boiling point samples are not adsorbed well in the adsorption tube, it is difficult to accurately analyze them. Therefore, a high adsorption agent is packed into the adsorption tube at low temperature for accurate analysis. On the contrary, the high boiling point VOC sample is strongly adsorbed. Since it does not fall, there is a disadvantage that a significant decrease in adsorption performance with time.

Thus, the present invention was devised to solve the problems of the prior art as described above, by varying the concentration of the standard gas through various dilution times by configuring a dilution apparatus for mixing the standard gas and dilution gas in the quantitative analysis It is an object of the present invention to provide a sample analysis device using an ultra low temperature concentration system, which enables the sample to be analyzed more accurately.

In addition, another object of the present invention is to form a sapphire block which insulates the high temperature while effectively transferring the low temperature between the adsorption tube and the low temperature plate, thereby being strongly adsorbed to the adsorption tube as high temperature heat while maintaining the low temperature of the low temperature plate. An object of the present invention is to provide a sample analysis apparatus using an ultra low temperature concentration system, which allows a sample to be quickly detached.

In the above-described object, a sample analysis device for comparatively analyzing a sample to be analyzed with a standard gas, the sample analysis device is configured with a dilution device for diluting and supplying a standard gas, the dilution device is a standard gas and a dilution gas A standard gas supply line and a dilution gas supply line supplied to different lines; A flow rate controller for controlling the flow rate and speed of each gas supplied and installed on the standard gas supply line and the dilution gas supply line; A mixing chamber connected to the standard gas supply line and the dilution gas supply line to mix the supplied standard gas and the dilution gas; And a heating block configured between the mixing chamber and the flow rate regulator to heat each gas introduced into the mixing chamber.

The sample analyzing apparatus using the cryogenic concentration system includes a vacuum chamber for concentrating the sucked sample at a low temperature, the vacuum chamber comprising: a main body connected in communication with a cooler and a refrigerant pipe; An adsorption tube installed to penetrate the main body, a sample adsorbed therein, and a heating wire installed on an outer surface thereof; A low temperature plate installed between the suction pipe and the refrigerant pipe; And a sapphire block installed between the low temperature plate and the adsorption tube.

According to the sample analysis device of the present invention, the sample is analyzed by the concentration value of the standard gas diversified by analyzing and storing the concentration of each dilution standard gas in which the standard gas and the dilution gas are mixed at various mixing ratios by the dilution device in the quantitative analysis. There is an advantage that can be analyzed more accurately.

In addition, according to the present invention, the sapphire block formed between the adsorption tube and the low temperature plate effectively blocks the cryogenic temperature of the cooler to the adsorption tube and insulates and blocks the high temperature of the heating wire so as not to be transferred to the low temperature plate, thereby notifying temperature change in the low temperature plate. There is an advantage that the sample can be quickly desorbed from the adsorption tube as a high temperature heat without.

1 is a block diagram of a sample analysis apparatus using the cryogenic concentration system according to the present invention.
Figure 2 is a cross-sectional configuration of the vacuum chamber configured in the sample analysis device using the cryogenic concentration system according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

First, in the reference numerals to the components shown in each drawing of the present invention, it should be noted that the same reference numerals as much as possible even if shown on the other drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

1 and 2 are views showing the configuration of a sample analyzing apparatus according to the present invention.

As shown in FIG. 1, the sample analyzing apparatus 1 of the present invention is a device for comparing and analyzing a sample to be analyzed with a standard gas, and diluting the standard gas with a vacuum chamber 10 for concentrating a sucked sample at low temperature. And a dilution device 50 for feeding.

In addition, a plurality of ST valves 20, 21, 22, a detector 30, and a vacuum pump 40 (suction pump, hereinafter) are provided between the vacuum chamber 10 and the dilution apparatus 50. "Vacuum pump" is connected to each line.

Meanwhile, the ST valves 20 and 21 and 22 illustrated in the drawings illustrate three-position ST valves for convenience, but the present invention is not limited thereto or may be variously modified.

The first ST valve 20 shown in FIG. 1 is connected through a dilution standard gas supply line 26 and a sample supply line 25 capable of gas transfer to the standard gas supply side dilution device 50 and the sample supply side, respectively.

The second ST valve 21 connected to the first ST valve 20 by a separate connection line 23 capable of gas transfer has a vacuum pump 40 (a suction pump, hereinafter referred to as a “vacuum pump”) and a carrier gas supply side. And a vacuum line 41, a carrier gas supply line 24, and a connection line 23 capable of gas transfer to the detector 30, respectively. At this time, the flow rate regulator 42 is installed on the vacuum line 41.

The third ST valve 22 connected to the second ST valve 21 by a separate connection line 23 capable of gas transfer is connected to the vacuum chamber 10 through a separate connection line 23 capable of gas transfer. .

On the other hand, these ST valves 20, 21, 22, the connection line 23, the flow rate regulator 42 is a component commonly used in the art, in particular ST valve 20 (21) (22) Is a device that can change the flow path while the upper end is rotated by a rotating means (not shown) by the electrical signal of the control unit, the configuration, function, operation and sequence control of the ST valve 20, 21, 22 is generally This is the matter.

Here, since the above-described connection line 23 has the same function, the same reference numerals are used to describe the key.

As shown in FIG. 1, the dilution apparatus 50 is connected to a standard gas supply line 51 to which standard gas is transferred and supplied to one port thereof, and a dilution gas supply to which the dilution gas is supplied is supplied to the other port. The line 53 is connected, and the opposite side of the standard gas supply line 51 and the dilution gas supply line 53 is connected to the mixing chamber 56.

Therefore, the standard gas and the dilution gas through the standard gas supply line 51 and the dilution gas supply line 53 are mixed in the mixing chamber 56.

On the other hand, on the standard gas supply line 51 and the dilution gas supply line 53, flow rate regulators 52 and 54 for adjusting the flow rate and speed of the gas supplied to the mixing chamber 56, respectively, A heating block 55 is installed between the flow rate regulators 52 and 54 and the mixing chamber 56 to induce smooth mixing of the gas by heating and activating the gas supplied to the mixing chamber 56. The block 55 and the flow rate regulators 52 and 54 are controlled by a controller (not shown), and the heating block 55 senses the temperature of the heating block 55 and applies the detection signal to the controller. Preferably, a temperature sensor (not shown) is installed.

Therefore, the standard gas and the dilution gas (hereinafter referred to as "dilution standard gas") mixed in the mixing chamber 56 as described above can form dilution standard gas of different concentrations by changing the dilution factor, that is, the mixing ratio. Standard gases enable more accurate and accurate analysis of sample concentrations.

For example, in the prior art, the concentration of a sample was analyzed based on a standard gas having a concentration of 100. In the present invention, the concentration of the sample is more accurately based on the concentration value of a standard gas having a concentration of 10, 100, or 200. It can be analyzed.

On the other hand, the standard gas and the dilution gas to be mixed in the mixing chamber 56 of the present invention may be mixed in the mixing process by the osmotic phenomenon.

As shown in FIG. 2, the vacuum chamber 10 uses a pulse tube cooler method to implement cryogenic temperatures of −180 ° C. or less. In this case, the refrigerant of the cooler 17 is helium. ) By using the gas, cooling to around -200 ° C is possible.

The vacuum chamber 10 includes a main body 11 connected in communication with a cooler 17 and a refrigerant pipe 16, and an adsorbent that is installed to penetrate the inside of the main body 11 and adsorbs a sample therein. The outer surface is provided with an adsorption tube 12, the heating wire 13 is installed, the cold plate 15 and the cold plate 15 and the adsorption tube installed between the adsorption tube 12 and the refrigerant tube 16 And a sapphire block 14 provided between (12).

The adsorption tube 12 is penetrated through the main body 11 and is connected to each end of the third ST valve 22 by connecting lines 23 at both ends thereof.

In the vacuum chamber 10 configured as described above, the refrigerant of the cooler 17 acts on the low temperature plate 15 inside the body 11 through the coolant tube 16 to lower the temperature of the low temperature plate 15 to cryogenic temperature. The cryogenic temperature is transferred to the adsorption tube 12 through the sapphire block 14 installed on the low temperature plate 15 so that the sample flowing in the adsorption tube 12 can be concentrated at low temperature.

At this time, the sapphire block 14 is to effect the low temperature while effectively transferring the low temperature, is installed on the low temperature plate 15 to a thickness of 1 to 3mm, the low temperature concentrated in the adsorption tube 12 In order to desorb the sample, the high temperature heat of the adsorption tube 12 through the hot wire 13 is prevented from being transferred to the low temperature plate 15. Such sapphire block 14 is a component generally used in the art.

The operation of the sample analyzer of the present invention configured as described above will be described.

<Dilution standard gas adsorption process>

The standard gas and the dilution gas supplied to the standard gas supply line 51 and the dilution gas supply line 53 are respectively adjusted by the flow rate through the flow rate regulators 52 and 54 and then heated by the heating block 55. While being supplied to the mixing chamber 56 and mixed. The dilution standard gas, which is the mixed gas mixed as described above, may be mixed at various concentrations by varying the dilution factor, that is, the mixing ratio, and the dilution standard gas thus mixed is discharged from the mixing chamber 56.

At this time, the controller sets the flow paths of the ST valves 20, 21, 22 as follows. The flow path of the first ST valve 20 is connected to the dilution standard gas supply line 26 and the connection line 23 (the sample supply line 25 is blocked), and the flow path of the second ST valve 21 is the vacuum line. The connection line 23 and 41 are in communication with each other (the connection line 23 of the carrier gas supply line 24 and the detector 30 is blocked), and the flow path of the third ST valve 22 is connected to all the connection lines 23. ) Is set to communicate.

The dilution standard gas discharged from the mixing chamber 56 while the flow path is secured is the first, second and third ST valves 20 and 21 through the dilution standard gas supply line 26 and the connection line 23. After passing through the 22 and passing through the adsorption tube 12 of the vacuum chamber 10, the dilution standard gas is adsorbed and collected by the adsorbent in the adsorption tube 12 maintained in the cryogenic state.

<Dilution Standard Gas Thermal Desorption Process>

The control unit sets the flow paths of the ST valves 20, 21, 22 as follows. The flow path of the first ST valve 20 cuts off all the lines, and the flow path of the second ST valve 21 connects the carrier gas supply line 24 with the connection line 23 and the connection line 23 on the detector 30 side. ) Is communicated (the vacuum line 41 is blocked), and the flow path of the third ST valve 22 is set such that all the connection lines 23 communicate.

At this time, the heating wire 13 wound around the adsorption tube 12 of the vacuum chamber 10 generates heat to provide high temperature heat to the adsorption tube 12, so that the diluted standard gas adsorbed in the adsorption tube 12 is desorbed. .

Therefore, the desorbed dilution standard gas is transferred to the detector 30 by the carrier gas moving along the flow path secured as described above, and the concentration of each dilution standard gas is analyzed, and then data is stored.

Analysis of the dilution standard gas, that is, adsorption and thermal desorption, is performed for each dilution standard gas prepared at different concentrations.

<Sample adsorption process>

The control unit sets the flow paths of the ST valves 20, 21, 22 as follows. The flow path of the first ST valve 20 communicates with the sample supply line 25 and the connection line 23 (the dilution standard gas supply line 26 is blocked), and the flow path of the second ST valve 21 is a vacuum line. The connection line 23 and 41 are in communication with each other (the connection line 23 of the carrier gas supply line 24 and the detector 30 is blocked), and the flow path of the third ST valve 22 is connected to all the connection lines 23. ) Is set to communicate.

As described above, the first, second, and third ST valves 20, 21, and 22 are sampled through the sample supply line 25 and the connection line 23 by the vacuum pressure of the vacuum pump 40 while the flow path is secured. ) Is passed through the adsorption tube 12 of the vacuum chamber 10, and the sample is adsorbed and collected by the adsorbent inside the adsorption tube 12 maintained in a cryogenic state.

Sample thermal desorption process

The control unit sets the flow paths of the ST valves 20, 21, 22 as follows. The flow path of the first ST valve 20 cuts off all the lines, and the flow path of the second ST valve 21 connects the carrier gas supply line 24 with the connection line 23 and the connection line 23 on the detector 30 side. ) Is communicated (the vacuum line 41 is blocked), and the flow path of the third ST valve 22 is set such that all the connection lines 23 communicate.

At this time, similar to the thermal desorption process of the diluting standard gas, the heating wire 13 wound around the adsorption tube 12 of the vacuum chamber 10 generates heat to provide high temperature heat to the adsorption tube 12 to thereby absorb the inside of the adsorption tube 12. The adsorbed sample is desorbed. At this time, since the high heat of the hot wire 13 is not transferred to the low temperature plate 15 by the sapphire block 14, the low temperature plate 15 can maintain a cryogenic state. This action also occurs in the thermal desorption process of dilute standard gas.

Therefore, the desorbed sample is transferred to the detector 30 by the carrier gas moving along the flow path secured as described above, and the concentration of the sample is analyzed and compared with each concentration value of the stored dilution standard gas.

1: Sample Analysis Device 10: Vacuum Chamber
11 main body 12 adsorption tube
13: heating wire 14: sapphire block
15: low temperature plate 16: refrigerant tube
17: cooler 20, 21, 22: ST valve
23: connection line 24: carrier gas supply line
25: sample supply line 26: dilution standard gas supply line
30 detector 40 vacuum pump
41: vacuum line 42: flow rate controller
50: dilution unit 51: standard gas supply line
52: flow rate regulator 53: dilution gas supply line
54: flow rate controller 55: heating block
56: mixing chamber

Claims (2)

In the sample analysis device that compares the sample to be analyzed with the standard gas,
The sample analysis device comprises a dilution device for diluting and supplying a standard gas,
The dilution apparatus includes a standard gas supply line and a dilution gas supply line, in which standard gas and dilution gas are supplied to different lines;
A flow rate controller for controlling the flow rate and speed of each gas supplied and installed on the standard gas supply line and the dilution gas supply line;
A mixing chamber connected to the standard gas supply line and the dilution gas supply line to mix the supplied standard gas and the dilution gas; And
And a heating block configured between the mixing chamber and the flow rate regulator to heat each gas introduced into the mixing chamber.
The method according to claim 1,
The sample analysis device comprises a vacuum chamber for concentrating the sucked sample at low temperature,
The vacuum chamber may include a main body connected in communication with a cooler and a refrigerant pipe;
An adsorption tube installed to penetrate the main body, a sample adsorbed therein, and a heating wire installed on an outer surface thereof;
A low temperature plate installed between the suction pipe and the refrigerant pipe; And
And a sapphire block installed between the low temperature plate and the adsorption tube.

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