A method for detecting trace water by gas chromatography and a ha-mr chromatographic column used thereby

Abstract

The application is a kind of trace water gas chromatography detection method and the HA-MR chromatographic column used therein, the detection system adopts integrated design, including the standard gas configuration system, sample gas flow path system, water generating system and gas chromatograph connected by pipeline, the HA-MR chromatographic column is a chromatographic column filled by crosslinked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial grade divinylbenzene and then modified by acidification, the mixed gas of hydrogen and oxygen generates water vapor state moisture standard gas in real time and continuously after passing through the DeOxis chromatographic column of the water generating system, and the water peak response signal is obtained by the gas chromatograph, the standard working curve between the water peak response signal and the moisture standard gas concentration is established, the concentration value of trace water in the sample gas is obtained by substituting the sample gas water peak response signal obtained by the gas chromatograph into the standard working curve, which not only realizes the detection of moisture by gas chromatography, but also solves the problem of poor stability of moisture standard gas.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of trace moisture detection method, in particular to a kind of trace moisture gas chromatography detection method and the HA-MR chromatographic column used in it, mainly applied to environmental detection, petrochemical industry, natural gas and many other fields of gas detection. BACKGROUND

[0002] In actual industry and laboratory, the main purpose of detecting trace moisture is to ensure the quality of product, the stability of process and the safety of equipment, but the determination of trace moisture in gas has always been a difficult problem, because water calibration is difficult, unstable and difficult to store.

[0003] At present, the main detection method of trace moisture adopts Karl Fischer method, dew point method, optical cavity ring-down spectroscopy method, etc., among which the technology closest to gas chromatography is optical cavity ring-down spectroscopy, which can detect trace moisture of 10 -9 mol / mol level, which is a laser absorption spectrum, which uses multiple reflections and interference of light in the cavity to measure the intensity and wavelength information of the output light signal for spectral analysis and material property research. However, due to the interference of impurities in the optical cavity ring-down spectrometer, the Karl Fischer moisture meter is usually a more common choice, which is a water determination technology based on iodometric method, its core principle is to use water to participate in the redox reaction of iodine (I2) and sulfur dioxide (SO2) to generate stable compounds with the help of pyridine and methanol, and the water content is determined quantitatively by titration or electrolysis. However, this method is not suitable for direct detection of gas matrix, and needs special treatment, and is easily affected by interfering substances. The dew point method has slow response and decreased precision at low dew point (high purity gas), and is easily affected by condensation point judgment.

[0004] Gas chromatography is a chromatographic separation and analysis method using gas as mobile phase. Sample gas is carried into the chromatographic column by carrier gas (mobile phase). Because the fixed phase in the column and the molecules of each component in the sample gas have different interaction forces, each component flows out of the chromatographic column at different times, thereby realizing the separation of each component. Gas chromatograph is widely used in laboratory and on-site industrial application because of its strong anti-interference ability, fast response and accurate measurement. However, it is difficult to detect moisture by gas chromatography, and there are significant technical bottlenecks:

[0005] 1. Poor stability of water standard gas: The existing water standard gas needs to be prepared in advance, and is easily affected by container adsorption and environmental humidity during storage, resulting in concentration drift and affecting the accuracy of detection results;

[0006] 2. Serious water peak tailing: Water peak tailing effect leads to decreased separation degree of other components and significantly reduced detection effect;

[0007] 3. Complex gas detection is limited: it is difficult for gas chromatography to detect moisture, which greatly damages the chromatographic column, and there is a lack of effective separation of water and common corrosive and interfering components (such as H2S, SO2, CO2, NH3, low molecular weight alcohols, etc.) chromatographic method, resulting in co-elution or peak interference.

[0008] Therefore, at present, the market still mostly adopts moisture meters for detection, but the use of moisture meters for detection has the following problems and defects that cannot be solved:

[0009] 1. Detection background is limited: conventional moisture meters cannot detect trace moisture in all backgrounds, such as being unable to detect moisture in corrosive gases;

[0010] 2. Limited detection types: moisture meters can only detect moisture, and the detection of other components requires separate purchase. SUMMARY

[0011] The purpose of the present application is to solve the problems and defects of the prior art, and to design a trace water gas chromatography detection method and the HA-MR chromatographic column used thereby, by setting a water standard gas preparation system at the front end of the sample gas inlet of the gas chromatograph, generating stable low-concentration water standard gas in real time, and combining a chromatographic column for separating water and gas components and a high-sensitivity detector, to realize the detection of trace water in various gases.

[0012] The present application is implemented as follows: a trace water gas chromatography detection method and the HA-MR chromatographic column used thereby, the detection system of the trace water gas chromatography detection method comprises a standard gas configuration system, a sample gas flow path system, a water generation system and a gas chromatograph connected by pipelines, and the detection method comprises the following specific steps:

[0013] S1, system preparation and standard gas generation path activation, the detection system is started and the standard gas generation path is activated by the gas path system switching valve, so that the system reaches a stable working state;

[0014] S2, real-time generation of moisture standard gas, hydrogen H2, oxygen O2 and balance gas are mixed into the water generation system HA-GS through the standard gas configuration system, and the catalytic reaction occurs at a set temperature through the DeOxis chromatographic column, the reaction chemical formula is 2H2+ O2→ 2H2O, and the moisture standard gas in the state of water vapor is generated in real time and continuously, wherein the standard gas configuration system generates different concentrations of standard gas by changing the ratio of hydrogen H2 and oxygen O2, and then generates moisture standard gas with different concentrations, the generated moisture standard gas enters the GC sample inlet of the gas chromatograph through the anti-adsorption transmission pipeline, the DeOxis chromatographic column is a deoxidizing column filled with 5A molecular sieve carrier loaded with active metal, which is used to generate water standard gas from hydrogen H2 and oxygen O2 at high temperature (280℃) with high efficiency and speed, and the active metal includes palladium, platinum or nickel;

[0015] S3, moisture standard gas detection and calibration curve establishment, the moisture standard gas enters the gas chromatograph through the GC sample inlet, is separated by the HA-MR chromatographic column, and the water component after separation enters the high-sensitivity non-destructive detector for detection to obtain the water peak response signal, the water peak response signal includes water peak retention time, peak height and peak area, a series of different concentrations of moisture standard gas are generated by changing the ratio of hydrogen H2 and oxygen O2 in step S2, and repeated sample detection is performed to establish the standard working curve between the water peak response signal and the concentration of the moisture standard gas, and the HA-MR chromatographic column is a chromatographic column filled with crosslinked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial-grade divinylbenzene and then acid-modified as a carrier;

[0016] S4, sample gas detection path activation and sampling, the switching valve system provided by the gas path system is switched to the sample gas detection path, the unknown concentration of gas sample gas to be detected is introduced through the sample gas flow path system, and enters the GC sample inlet of the gas chromatograph through the anti-adsorption transmission pipeline, and the sample gas is introduced into the gas chromatograph for detection;

[0017] S5, sample gas separation and moisture detection, the sample gas is introduced into the GC sample inlet of the gas chromatograph, and is also separated on the HA-MR chromatographic column, and the water peak retention time determined in step S3 is used for qualitative analysis, and the water peak after separation enters the high-sensitivity non-destructive detector for detection to obtain the water peak response signal;

[0018] S6, moisture quantitative analysis, the sample gas water peak response signal measured in step S5 is substituted into the standard working curve established in step S3 by the data processing and analysis system of the gas chromatograph, the concentration value of trace water in the sample gas is obtained, and the result is output.

[0019] Further, the gas chromatograph in step S1 is set to a carrier gas flow of 30 mL / min, and a column temperature of 50°C, and the water generating system HA-GS is set to a catalytic reaction temperature of 280°C.

[0020] Further, the mixed gas in step S2 first flows through the built-in water removal module in the water generating system to completely remove the background moisture, and then the purified mixed gas containing hydrogen H2 and oxygen O2 enters the DeOxis column.

[0021] Further, the sample gas in step S4 is switched and controlled by the switching valve system of the gas path system to enter the water generating system HA-GS and then pass through the anti-adsorption transmission pipeline to enter the GC sample inlet of the gas chromatograph. At this time, the water generating system HA-GS is switched to the closed and stopped working state by the internal switching valve, and only the sample gas flow path is reserved.

[0022] Further, in the real-time generation of the moisture standard gas in step S2, the proportion of hydrogen H2 or oxygen O2 is adjusted by using the dilution instrument connected to the standard gas configuration system to generate standard gases of different concentrations. The dilution gas used by the dilution instrument is the same inert gas as the equilibrium gas in step S2.

[0023] The HA-MR column used in the micro water gas chromatography detection method is a column prepared by loading a carrier modified by acidification of cross-linked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial-grade divinylbenzene. The acidification method is as follows: first, uniformly disperse the cross-linked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial-grade divinylbenzene in a container containing anhydrous ethanol, and slowly and batchwise add ≥95% concentrated sulfuric acid to the container in an ice water bath. Then, transfer the entire container to a constant temperature water bath with a temperature of 70°C for 4 hours. Then, wash and dry the acid-modified carrier, and finally load it into the column to obtain the HA-MR column.

[0024] Further, in the acidification method, the concentrated sulfuric acid is slowly added to the container containing the cross-linked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial-grade divinylbenzene in at least five times. After each addition is completed, wait for the reaction system temperature to drop below 40°C before performing the next addition of concentrated sulfuric acid.

[0025] Further, in the acidification method, the acid-modified carrier is washed to a pH value of ≥6.0, which is weakly acidic to neutral, and then dried.

[0026] The beneficial effects of the present application are: the present application innovatively uses gas chromatography to determine moisture, and integrates the moisture standard gas preparation system with the gas chromatograph to realize real-time generation of moisture standard gas and accurate detection of trace moisture. The problems of poor stability of moisture standard gas and the inability of gas chromatography to detect moisture in the prior art are solved.

[0027] The present application breaks through the technical bottleneck of detecting moisture in the field of gas chromatography. First, the mixed gas of hydrogen (H2) and oxygen (O2) with different proportions is configured as a standard gas by a standard gas configuration system in the moisture standard gas preparation system. Then, the background moisture is completely removed by a water removal module in the water generation system HA-GS (Hydration-Generation System) in the moisture standard gas preparation system. Then, the moisture standard gas is prepared in real time, stably and continuously after passing through the DeOxis chromatographic column, avoiding the problems of storage loss and concentration drift. The key problems of poor storage stability and concentration drift of traditional static moisture standard gas are solved, providing a traceable, highly stable online calibration method for trace water detection.

[0028] The chromatographic column for separating moisture and gas components in the present application is a HA-MR chromatographic column (i.e. a chromatographic column filled with crosslinked copolymer microspheres as a carrier, which are synthesized by suspension copolymerization of acid-modified styrene and industrial-grade divinylbenzene). Through specific selectivity and optimized chromatographic conditions, the moisture and other components in the sample gas are separated, eliminating the interference caused by substances other than moisture in the detection of moisture, and having excellent anti-interference performance. The water peak shape is significantly improved (reducing tailing), and water and common permanent gases (such as N2, O2, CH4, CO, CO2) and various corrosive and interfering components (such as H2S, SO2, NH3) are effectively separated, significantly improving the accuracy and anti-interference ability of the detection, and the detection limit can reach 10 -9 mol / mol level, and is especially suitable for multi-component synchronous analysis of corrosive gases and permanent gases (such as N2, O2, CO2, etc.).

[0029] The present application realizes the detection of trace moisture in sample gas containing corrosive gas, permanent gas and oxygen-containing compound, and can detect other gas components in addition to moisture with one machine, reducing cost and being suitable for industries sensitive to moisture such as semiconductors, natural gas, petrochemical industry, etc. At the same time, the present application adopts integrated design and automatic control, reducing manual intervention in the detection process, reducing human error, sample gas transmission loss and adsorption, improving detection efficiency and reliability of the results, and realizing "one-key" or programmed operation of trace moisture analysis in gas. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1A micro water gas chromatography detection system structure block diagram adopted by the present application.

[0031] Figure 2 A standard working curve chromatogram between peak height and moisture standard gas concentration of an embodiment of the present application.

[0032] Figure 3 A sample gas moisture detection linear graph of an embodiment of the present application. DETAILED DESCRIPTION

[0033] The present application will be further described below in conjunction with the drawings and specific embodiments.

[0034] According to the drawings Figure 1 , the present application is a kind of micro water gas chromatography detection method and the HA-MR chromatographic column used by it, the detection method adopts the detection system including the standard gas configuration system, sample gas flow path system, water generation system and gas chromatograph connected by pipeline, the standard gas and the sample gas to be measured configured by the standard gas configuration system are respectively through the gas path system sequentially into the water generation system into the gas chromatograph for analysis and detection, the gas path system includes the gas path pipeline into the water generation system, the carrier gas system arranged in the gas chromatograph and the switching valve system arranged on the gas path and other gas flow direction and flow control device, the specific detection steps are as follows:

[0035] S1, system preparation and standard gas generation path activation

[0036] Start the gas chromatograph, set the carrier gas flow 30 mL / min, the chromatographic column temperature 50 DEG C, start the water generation system (HA-GS), set the catalytic reaction temperature 280 DEG C, activate the switching valve system in the gas path system to switch to "standard gas generation path", make the system reach stable working state, prepare for generating moisture standard gas.

[0037] S2, real-time generation of moisture standard gas and background purification

[0038] A mixture of hydrogen H2, oxygen O2 and balance gas is introduced into a water generation system (HA-GS). The balance gas is an inert gas. The mixture of hydrogen H2 and oxygen O2 first flows through a water removal module built in the water generation system to completely remove the background moisture. The purified mixture of hydrogen H2 and oxygen O2 enters a DeOxis chromatographic column to generate water vapor state moisture standard gas in real time and continuously at a set temperature through a catalytic reaction (2H2 + O2→ 2H2O). Different concentrations of standard gas can be generated by changing the ratio of hydrogen H2 and oxygen O2, and then moisture standard gas with different concentrations can be prepared. The generated moisture standard gas directly enters the GC injection port of the gas chromatograph through the anti-adsorption transmission pipeline. The DeOxis chromatographic column is a deoxidizing column filled with 5A molecular sieve support loaded with active metals, such as palladium, platinum or nickel, for efficient and rapid generation of water standard gas from hydrogen H2 and oxygen O2 at high temperature (280℃).

[0039] S3, moisture standard gas detection and calibration curve establishment

[0040] The moisture standard gas enters the gas chromatograph through the GC injection port of the gas chromatograph, is separated by the HA-MR chromatographic column, and the separated water component enters the high-sensitivity non-destructive detector for detection to obtain the water peak response signal, including the water peak retention time and the peak height or peak area. A series of different concentrations of moisture standard gas are generated by changing the ratio of hydrogen H2 and oxygen O2 in step S2 to perform repeated sample detection, and a standard working curve between the peak height or peak area in the water peak response signal and the moisture standard gas concentration is established. The real-time generated moisture standard gas is used to establish the quantitative calibration basis under the current instrument state, which can effectively avoid the instability problem of traditional moisture standard gas.

[0041] S4, sample gas detection path activation and sampling

[0042] The switching valve system of the gas path system is switched to the "sample gas detection path". The gas sample with unknown concentration to be detected is introduced through the sample gas flow path system. The sample gas is controlled by the switching valve system of the gas path system to flow through the water generation system (HA-GS) and then enter the GC injection port of the gas chromatograph through the anti-adsorption transmission pipeline. At this time, the water generation system (HA-GS) is switched by the internal switching valve to only retain the sample gas flow path, and the moisture standard gas generation path of the water generation system is in a closed and stopped working state. The sample gas can also be directly introduced into the GC injection port of the gas chromatograph through the anti-adsorption transmission pipeline by switching the switching valve system of the gas path system, and the sample gas is introduced into the gas chromatograph for detection.

[0043] S5, sample gas separation and moisture detection

[0044] After the sample gas is introduced into the GC inlet of the gas chromatograph, it is also separated on the HA-MR column. Qualitative analysis is performed using the water peak retention time determined in step S3. The separated water peak is detected by a high-sensitivity non-destructive detector to obtain the peak height or peak area in the water peak response signal.

[0045] S6, moisture quantitative analysis

[0046] According to the standard working curve established in step S3, the peak height or peak area in the water peak response signal of the sample gas measured in step S5 is substituted into the standard working curve by the data processing and analysis system of the gas chromatograph, and the concentration value of the trace water in the sample gas is obtained and the result is output.

[0047] According to the attached Figure 1 , the detection system for the trace water gas chromatography detection method, comprising a moisture standard gas preparation system, a sample gas flow path system and a gas chromatograph connected by a pipeline, the moisture standard gas preparation system comprising a standard gas configuration system and a water generation system, the standard gas configured by the standard gas configuration system and the sample gas passing through the gas path system in sequence through the water generation system into the gas chromatograph for analysis and detection.

[0048] 1. Standard gas configuration system

[0049] By changing the ratio of hydrogen H2 and oxygen O2, a standard gas composed of a mixture of hydrogen H2, oxygen O2 and balance gas with different proportions is configured, and the specific proportion value of the two is determined each time, which provides a basis for subsequent moisture conversion and calibration.

[0050] In the detection method, the ratio of hydrogen H2 or oxygen O2 can also be adjusted by connecting a diluter to the standard gas configuration system to generate standard gases with different concentrations. The diluter uses the same inert gas as the balance gas.

[0051] 2. Sample gas flow path system

[0052] The sample gas to be tested passes through the sample gas flow path system, the gas path system and the water generation system (HA-GS) in sequence and enters the gas chromatograph for detection.

[0053] 3. Gas path system

[0054] The gas path system includes gas path pipelines into the water generation system (HA-GS), carrier gas systems set inside the gas chromatograph, and flow direction and flow control devices set on the gas path.

[0055] 4. Water generation system (HA-GS)

[0056] The water generation system (HA-GS) is internally provided with a DeOxis chromatographic column, a water removal module and a temperature control system.

[0057] Working principle: The standard gas configured by the standard gas configuration system is first introduced into the water removal module of the water generation system through the gas path system to remove the background water, and then enters the DeOxis chromatographic column to generate moisture standard gas (H2O). The standard gas configuration system adjusts the proportion of H2 and O2 by controlling the hydrogen concentration, and then the water generation system (HA-GS) accurately generates moisture standard gas with corresponding concentration.

[0058] 5. Gas chromatograph

[0059] The gas chromatograph is provided with a HA-MR chromatographic column for separating moisture from other gas components, and a high-sensitivity non-destructive detector. Each module of the gas chromatograph is connected by an anti-adsorption pipeline to avoid moisture adsorption and simplify the heat preservation requirement. The sample gas or moisture standard gas is switched into the HA-MR chromatographic column through the switching valve system provided in the gas path system to realize quantitative sampling. The high-sensitivity non-destructive detector includes a pulsed discharge helium ion detector.

[0060] The HA-MR chromatographic column is a chromatographic column filled with cross-linked copolymer microspheres of styrene and industrial-grade divinylbenzene synthesized by suspension copolymerization and then acid-modified as a carrier. The acid-modification method is to uniformly disperse the cross-linked copolymer microspheres of styrene and industrial-grade divinylbenzene synthesized by suspension copolymerization in a container containing anhydrous ethanol, and in an ice water bath, at least five times of concentrated sulfuric acid with a concentration greater than or equal to 95% is slowly added to the container. After each addition is completed, wait for the reaction system temperature to drop below 40℃, and then perform the next concentrated sulfuric acid addition operation. After all the concentrated sulfuric acid is added, the container is transferred to a constant temperature water bath kettle, the temperature is 70℃, and it is kept for 4 hours. Then the acid-modified carrier is washed to a pH value ≥ 6.0, showing weakly acidic to neutral state, and then dried to obtain the acid-modified cross-linked copolymer microspheres of styrene and industrial-grade divinylbenzene synthesized by suspension copolymerization, which is finally packed into the chromatographic column as a carrier to obtain the HA-MR chromatographic column.

[0061] 6. Integrated design

[0062] The water generation system in the detection system is installed in the auxiliary box and directly connected to the sample inlet of the gas chromatograph through the pipeline to reduce the gas transmission loss. The supporting software system (such as gas chromatograph workstation) synchronously controls the gas flow, catalytic temperature of the water generation system and the separation program of the chromatograph to realize automatic detection.

[0063] The method is used for testing water in six kinds of permanent gases (high-purity hydrogen, high-purity nitrogen, high-purity oxygen, high-purity sulfur hexafluoride, high-purity helium, and high-purity carbon dioxide with a purity of 99.999%), and the test results are compared with the test results of a water meter (a British ALPHA trace moisture meter). For example, for high-purity helium, the test result of the gas chromatography detection method is 0.67*10 -6 mol / mol, and the test result of the water meter is 0.65*10 - 6 mol / mol, which proves the effectiveness of the method.

[0064] Embodiment

[0065] Appendix Figure 2 and Appendix Figure 3 are specific steps of the detection method according to the application, and the water test result of the sample gas is 10*10 -9 mol / mol, and the linear graph.

[0066] In this embodiment, a HA-9560 gas chromatograph produced by Shanghai Huai Chromatography Technology Co., Ltd. is used. First, a bottle of hydrogen with a concentration of 5*10 -6 mol / mol and a bottle of oxygen with a concentration of 100*10 -6 mol / mol are configured, the mixed gas after being connected to the standard gas configuration system is introduced into a water generation system (HA-GS) to generate water standard gas, and by changing the proportion of H2 and O2 introduced, water standard gas with different concentrations is obtained. In this embodiment, water standard gas with concentrations of 1*10 -6 mol / mol, 0.5*10 -6 mol / mol, 0.1*10 -6 mol / mol, 0.05*10 -6 mol / mol, 0.01*10 -6 mol / mol is generated, and the response values (peak height is used in this embodiment) at different concentrations are obtained through gas chromatograph analysis and detection, a standard working curve between the peak height in the water peak response signal and the concentration of the water standard gas is established, and the linear results R2=0.9999 are output by the gas chromatograph according to Appendix Figure 3 , which shows that the method can obviously improve the water tailing condition, and the detection limit can reach 0.01*10 -6 mol / mol. Since the carrier gas of the gas chromatograph is usually helium, in order to avoid interference in subsequent detection, the dilution gas and the equilibrium gas in this embodiment are also helium. The dilution instrument is a dynamic dilution instrument, such as a HA-11 dynamic dilution instrument produced by Shanghai Huai Chromatography Technology Co., Ltd.

Claims

1. A method for detecting trace water by gas chromatography, characterized in that: The detection system used in the detection method includes a standard gas configuration system, a sample gas flow system, a water generation system, and a gas chromatograph connected by pipelines. The specific steps of the detection method are as follows: S1: System preparation and standard gas generation path activation: The detection system is started and the standard gas generation path is activated through the gas system switching valve to enable the system to reach a stable working state; S2. Real-time generation of moisture standard gas. A mixture of hydrogen H2, oxygen O2, and a balance gas is introduced into the water generating system HA-GS via the standard gas configuration system. A catalytic reaction occurs at a set temperature through the DeOxis chromatographic column. The reaction chemical formula is 2H2 + O2 → 2H2O, and moisture standard gas in a water vapor state is generated in real time and continuously. The standard gas configuration system generates standard gas of different concentrations by changing the ratio of the introduced hydrogen H2 and oxygen O2, thereby producing moisture standard gas of corresponding different concentrations. The generated moisture standard gas directly enters the GC inlet of the gas chromatograph through an anti-adsorption transmission line. The DeOxis chromatographic column is a deoxygenated column, which is a chromatographic column filled with a 5A molecular sieve support loaded with active metals; S3, moisture standard gas detection and calibration curve establishment, the moisture standard gas enters the gas chromatograph through the GC inlet of the gas chromatograph and is separated by the HA-MR chromatographic column, the separated water component enters the high-sensitivity non-destructive detector for detection, and obtains a water peak response signal, the water peak response signal including the water peak retention time, peak height and peak area, and then the ratio of hydrogen H2 and oxygen O2 in step S2 is changed to generate a series of moisture standard gases with different concentrations, and repeated sampling and detection are performed to establish a standard working curve between the water peak response signal and the concentration of the moisture standard gas, the HA-MR chromatographic column is a chromatographic column made by using cross-linked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial-grade divinylbenzene, which are acidified and modified and then used as a support for filling; S4. Activate and inject the sample gas detection path. Switch to the sample gas detection path through the switching valve system provided in the gas path system. Introduce the gas sample of unknown concentration to be measured through the sample gas flow path system and enter the GC inlet of the gas chromatograph through the anti-adsorption transmission line. The sample gas is introduced into the gas chromatograph for detection. S5. Sample gas separation and moisture detection: After the sample gas is introduced into the GC inlet of the gas chromatograph, it is also separated on the HA-MR chromatographic column and qualitatively analyzed using the water peak retention time determined in step S3. The separated water peak enters a high-sensitivity non-destructive detector for detection to obtain a water peak response signal; S6. Quantitative analysis of moisture: The data processing and analysis system of the gas chromatograph substitutes the sample gas water peak response signal measured in step S5 into the standard working curve established in step S3 to obtain the concentration value of trace water in the sample gas and output the result.

2. The gas chromatography detection method for trace water according to claim 1, characterized in that: In step S1, the gas chromatograph is started and set to have a carrier gas flow rate of 30 mL / min and a chromatographic column temperature of 50° C. The catalytic reaction temperature of the water generating system HA-GS is set to 280° C.

3. The gas chromatography detection method for trace water according to claim 1, characterized in that: In step S2, the mixed gas first flows through the water removal module built into the water generation system to completely remove the background moisture, and the purified mixed gas containing hydrogen H2 and oxygen O2 then enters the DeOxis chromatographic column. The active metal loaded on the 5A molecular sieve support in the DeOxis chromatographic column includes palladium, platinum or nickel.

4. The gas chromatography detection method for trace water according to claim 1, characterized in that: The sample gas in step S4 is switched by the switching valve system set in the gas path system to control the flow direction into the water generating system HA-GS and then enters the GC inlet of the gas chromatograph through the anti-adsorption transmission pipeline. At this time, the water generating system HA-GS is switched to a closed and stopped working state by the internal switching valve, leaving only the sample gas flow path.

5. The gas chromatography detection method for trace water according to claim 1, characterized in that: In the step S2, in which the moisture standard gas is generated in real time, the ratio of hydrogen H2 or oxygen O2 is adjusted by connecting a diluter to the standard gas configuration system to generate standard gases of different concentrations. The dilution gas used by the diluter and the balance gas described in step S2 are the same inert gas.

6. A HA-MR chromatographic column for use in the gas chromatography detection method for trace water according to any one of claims 1 to 5, characterized in that: The HA-MR chromatographic column is a chromatographic column prepared by using cross-linked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial-grade divinylbenzene, which are then acidified and modified and then used as a support. The acidification modification method is to first uniformly disperse the cross-linked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial-grade divinylbenzene in a container filled with anhydrous ethanol, and then slowly and batchwise add greater than or equal to 95% concentrated sulfuric acid to the container in an ice water bath, and then transfer the entire container to a constant temperature water bath pot at 70°C for 4 hours, and then wash and dry the acidified modified support, and finally fill it into the chromatographic column to obtain the HA-MR chromatographic column.

7. The HA-MR chromatographic column according to claim 6, characterized in that: In the acidification modification method, concentrated sulfuric acid is slowly added at least five times to a container containing cross-linked copolymer microspheres synthesized by suspension copolymerization of styrene and industrial-grade divinylbenzene. After each addition is completed, the reaction system temperature is allowed to drop below 40° C. before the next addition of concentrated sulfuric acid.

8. The HA-MR chromatographic column according to claim 6, characterized in that: In the acidification modification method, the acidified and modified support is washed until the pH value is greater than or equal to 6.0 and is in a weakly acidic to neutral state before being dried.

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