Electronic-grade liquid chlorine automatic analysis system and use method

Abstract

The invention relates to an electronic-grade liquid chlorine automatic analysis system and a use method, the system comprises a moisture analyzer and a gas chromatograph, the front of the moisture analyzer and the front of the gas chromatograph are respectively connected with a sample gas branch, a nitrogen branch and a helium branch through pipelines, a tail gas branch is also arranged behind the moisture analyzer, and the tail gas branch is connected with the nitrogen branch and the helium branch through pipelines. And a plurality of manual metal diaphragm valves and a plurality of pneumatic metal diaphragm valves are arranged on the pipeline. According to the method, manual participation is reduced in the detection process, personnel safety can be effectively guaranteed, personnel operation errors can be reduced, and the content of air impurities and moisture in the electronic-grade chlorine can be rapidly and safely detected in the analysis process.

Description

Technical Field

[0001] This invention belongs to the field of materials science and technology, and relates to an electronic-grade liquid chlorine automated analysis system and its usage method. Background Technology

[0002] With the rapid development of the semiconductor industry, represented by ultra-large-scale integrated circuits and panel displays, in the global high-tech field, large quantities of electronic-grade chlorine are required for various manufacturing processes such as etching and cleaning of silicon-based semiconductor materials. Chlorine is an extremely strong oxidizing agent, second only to fluorine in its reactivity. At room temperature and pressure, chlorine is a yellowish-green, irritating, and toxic gas, classified as a Class II hazardous chemical. The maximum inhalation concentration for humans is 2.5 mg / m³. 3 Inhalation of chlorine gas can be fatal. The maximum permissible concentration of chlorine gas in the air of workplaces and storage areas is 1 mg / m³. 3 The most obvious symptom of chlorine poisoning is severe coughing. In severe cases, pulmonary edema can occur, leading to respiratory and circulatory difficulties and death. Chlorine entering the body through the esophagus can cause nausea, vomiting, chest pain, and diarrhea. Chlorine leakage is a risk in production analysis, posing a significant threat to personnel and property safety. Furthermore, traditional analysis requires manual operation of valves to control pipeline routing. Electronic-grade hydrogen chloride has stringent specifications, and human error can lead to inaccurate analytical results and safety issues. Therefore, minimizing human intervention in analytical processes is a major challenge.

[0003] To address these issues, an automated electronic-grade liquid chlorine analysis system and its usage method were designed. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a simple and reasonable automated analysis system for electronic-grade liquid chlorine and its usage method. This invention reduces manual intervention during the detection process, effectively ensuring personnel safety and reducing human error. It can quickly and safely detect air impurities and moisture content in electronic-grade chlorine gas during analysis.

[0005] The present invention is achieved through the following technical solution: an electronic-grade liquid chlorine automated analysis system, which consists of a moisture analyzer and a gas chromatograph. The moisture analyzer and the gas chromatograph are respectively connected to a sample gas branch, a nitrogen branch and a helium branch through pipelines. A tail gas branch is also provided after the moisture analyzer. Multiple manual metal diaphragm valves and multiple pneumatic metal diaphragm valves are provided on the pipeline.

[0006] Preferably, the sample gas in the sample gas branch enters through a manual metal diaphragm valve MV01 and a pneumatic metal diaphragm valve AV02, then enters the gas chromatograph through a pneumatic metal diaphragm valve AV03, enters the moisture analyzer through a pneumatic metal diaphragm valve AV06, and is discharged to the tail gas branch through a pneumatic metal diaphragm valve AV08.

[0007] Preferably, the helium in the helium branch enters through manual metal diaphragm valve MV10, manual metal diaphragm valve MV02 and pneumatic metal diaphragm valve AV01, and is then discharged to the tail gas branch through pneumatic metal diaphragm valve AV08; after entering through manual metal diaphragm valve MV11 and manual metal diaphragm valve MV04, it is divided into two paths, one of which enters the gas chromatograph through MV03 as carrier gas and driving gas, and the other of which enters the gas chromatograph through AV04 as protective gas.

[0008] Preferably, the nitrogen in the nitrogen branch enters through manual metal diaphragm valves MV13 and MV08, and then enters the moisture meter as a protective gas through pneumatic metal diaphragm valve AV07.

[0009] Preferably, the gas chromatograph includes two 10-port valves and one 4-port valve, two quantitative loops, one DID detector, and four chromatographic columns. The seventh port of the first 10-port valve is the sample gas inlet, connected to the eighth port. A first quantitative loop 1 is located between the eighth and fifth ports. The fifth port is connected to the sixth port, and the sixth port is connected to the twelfth port of the second 10-port valve. The fourth port is the carrier gas 2 inlet, connected to the third port. A pre-separation column 1 is located between the third and ninth ports. The ninth port is connected to the tenth port, which is also a vent port. The first port is the carrier gas 1 inlet, connected to the second port. An analytical column 1 is located between the second port and the third port of the 4-port valve. The third port of the 4-port valve is connected to the fourth port, and the fourth port of the 4-port valve is connected to the DID detector.

[0010] Preferably, the twelfth and thirteenth ports of the second ten-way valve are connected, a second metering ring 2 is provided between the thirteenth and twentieth ports, the twentieth port is connected to the eleventh port, the nineteenth port is the inlet of the carrier gas 3, the nineteenth port is connected to the eighteenth port, the pre-separation column 2 is between the eighteenth and fourteenth ports, the fourteenth port is connected to the fifteenth port, and the eleventh and fifteenth ports are both vent ports; the sixteenth port is the inlet of the carrier gas 4, the sixteenth port is connected to the seventeenth port, the analysis column 2 is between the seventeenth port and the second port of the four-way valve, and the second port of the four-way valve is connected to the first port of the four-way valve, the first port of the four-way valve is also a vent port.

[0011] A method for using an automated electronic-grade liquid chlorine analysis system, the method comprising the following steps: 1. Pretreatment: The internal gas is purged by helium purging, and then sample gas is introduced; 2. After the sample gas is introduced, all the helium is purged to replace the helium with the sample gas. After the replacement is completed, the moisture analyzer is turned on to detect the moisture content. 3. After the moisture content is detected, the sample is analyzed by gas chromatography for final determination.

[0012] Preferably, the preprocessing method in step 1 is as follows: a. Open the pneumatic valve AV01 to introduce helium. If the pressure gauge PT01 reading increases, it indicates that the helium introduction was successful. If the introduction was successful, close the pneumatic valve AV01 after 10 seconds. Then open the vent valve AV09 and the vent valve AV08 to release the helium. If the PT01 reading is 0, it indicates that the venting was successful. Then close AV08 and AV09. b. Repeat steps a12-18 times to complete the helium replacement.

[0013] Preferably, the method for sample gas replacement in step 2 is as follows: c. Sample gas replacement: Open the pneumatic valve AV02 to introduce sample gas. If the pressure gauge PT01 reading increases, it indicates that the introduction of sample gas was successful. If the introduction was successful, close the pneumatic valve AV02 after 10 seconds, open the vent valve AV09, and then open the vent valve AV08 to discharge the sample gas. If the PT01 reading is 0, the venting was successful. Close AV08 and AV09. d. Repeat steps C3-5 times to complete the sample gas replacement; e. Normally open pneumatic valve AV02. Open pneumatic valve AV06 to allow sample gas to enter the moisture analyzer for analysis and detection. When the detected moisture content is less than 1 ppm, open AV03 to allow sample gas to enter the gas chromatograph for analysis and detection.

[0014] Preferably, the gas chromatograph analysis and detection method in step 3 is as follows: 1) At 0.01 minutes, pneumatic valve AV21 opens and AV22 closes. The sample gas enters the purge metering loop 1 and metering loop 2 from the seventh port and then exits from the twentieth port. 2) At 0.3 minutes, AV22 is turned on and AV21 is turned off. The sample gas is discharged through AV22. The first ten-way valve is switched to the quantitative loop 1 injection mode: the carrier gas 2 enters the backflush quantitative loop 1 from the fourth interface, enters the pre-column 1 from the ninth interface, and then enters the analytical column 1 through the third and second interfaces, and then enters the DID detector through the third interface of the four-way valve. 3) At 4 minutes, the 20th valve switches to the quantitative loop 2 injection mode: Carrier gas 3 enters the backflush quantitative loop 2 from the 19th port, enters the pre-column 2 from the 14th port, and then enters the analytical column 2 through the 17th and 18th ports; 4) At 5.5 minutes, the four-way valve switches to the column 2 injection mode, and the second port of the four-way valve is connected to the fourth port of the four-way valve to connect column 2 to the DID detector; 5) At 7.7 minutes, the four-way valve switches to the sample injection mode of the analysis column 1. The purpose is to cut off the chlorine gas in the analysis column 2 to the vent valve, so as to prevent chlorine gas from entering the DID detector and damaging the instrument. All valves are restored to their initial state before detection.

[0015] The beneficial effects of this invention are as follows: 1) The electronic-grade liquid chlorine automated analysis system and its usage method of the present invention are designed as an electronic-grade chlorine automatic analysis device that can realize remote analysis of electronic-grade chlorine, effectively avoiding human intervention and ensuring the safety of personnel; 2) This invention can form a standardized operation control procedure, avoiding human error; 3) The automated analysis method of this invention yields accurate and stable results, with no significant difference compared to the method in the national standard. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the overall structure of the present invention; Figure 2 This is the initial state diagram of the gas chromatograph in this invention; Figure 3 This is a diagram of the injection mode of the tenth valve of the gas chromatograph in this invention; Figure 4 This is a diagram of the injection mode of the 20th valve of the gas chromatograph of the present invention; Figure 5 This is the detection spectrum of the present invention. Detailed Implementation

[0017] To enable those skilled in the art to more clearly understand the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0018] In the description of this invention, it should be understood that the orientation or positional relationship indicated by terms such as "upper", "lower", "left", "right", "inner", "outer", "lateral", and "vertical" is based on the orientation or positional relationship shown in the accompanying drawings and is only for the convenience of describing this invention, and is not intended to indicate or imply that the device or component referred to must have a specific orientation, and therefore should not be construed as a limitation of this invention.

[0019] The invention will now be described in detail with reference to the accompanying drawings: Figure 1-4As shown, an electronic-grade liquid chlorine automated analysis system is provided. The system consists of a moisture analyzer and a gas phase analyzer. The moisture analyzer and the gas phase analyzer are respectively connected to a sample gas branch, a nitrogen branch, and a helium branch through pipelines. A tail gas branch is also provided at the rear of the moisture analyzer. Multiple manual metal diaphragm valves and multiple pneumatic metal diaphragm valves are provided on the pipeline.

[0020] The sample gas in the sample gas branch enters through the manual metal diaphragm valve MV01 and the pneumatic metal diaphragm valve AV02, then enters the gas chromatograph through the pneumatic metal diaphragm valve AV03, enters the moisture analyzer through the pneumatic metal diaphragm valve AV06, and is discharged to the tail gas branch through the pneumatic metal diaphragm valve AV08.

[0021] Helium in the helium branch enters through manual metal diaphragm valve MV10, manual metal diaphragm valve MV02 and pneumatic metal diaphragm valve AV01, and is then discharged to the tail gas branch through pneumatic metal diaphragm valve AV08; after entering through manual metal diaphragm valve MV11 and manual metal diaphragm valve MV04, it is divided into two paths, one of which enters the gas chromatograph through MV03 as carrier gas and driving gas, and the other of which enters the gas chromatograph through AV04 as protective gas. The nitrogen in the nitrogen branch enters through manual metal diaphragm valves MV13 and MV08, and then enters the moisture meter as a protective gas through pneumatic metal diaphragm valve AV07.

[0022] The gas chromatograph includes two 10-port valves and one 4-port valve, two quantitative loops, one DID detector, and four chromatographic columns. The seventh port of the first 10-port valve is the sample gas inlet, connected to the eighth port. A first quantitative loop 1 is located between the eighth and fifth ports. The fifth port is connected to the sixth port, and the sixth port is connected to the twelfth port of the second 10-port valve. The fourth port is the carrier gas 2 inlet, connected to the third port. A pre-separation column 1 is located between the third and ninth ports. The ninth port is connected to the tenth port, which is also a vent. The first port is the carrier gas 1 inlet, connected to the second port. An analytical column 1 is located between the second port and the third port of the 4-port valve. The third port of the 4-port valve is connected to the fourth port, and the fourth port of the 4-port valve is connected to the DID detector.

[0023] The twelfth and thirteenth ports of the second ten-way valve are connected, and a second quantitative ring 2 is provided between the thirteenth and twentieth ports. The twentieth port is connected to the eleventh port. The nineteenth port is the inlet of the carrier gas 3 and is connected to the eighteenth port. The pre-separation column 2 is located between the eighteenth and fourteenth ports. The fourteenth port is connected to the fifteenth port. Both the eleventh and fifteenth ports are vent ports. The sixteenth port is the inlet of the carrier gas 4 and is connected to the seventeenth port. The analysis column 2 is located between the seventeenth port and the second port of the four-way valve. The second port of the four-way valve is connected to the first port of the four-way valve, which is also a vent port.

[0024] A method for using an automated electronic-grade liquid chlorine analysis system, the method comprising the following steps: 1. Pretreatment: The internal gas is purged by helium replacement before sample gas is introduced; 2. After the sample gas is introduced, all the helium is purged to replace the helium with the sample gas. After the replacement is complete, the moisture analyzer is turned on to detect the moisture content. 3. After the moisture content is detected, the sample is analyzed by gas chromatography for final determination.

[0025] Preferably, the preprocessing method in step 1 is as follows: a. Open the pneumatic valve AV01 to introduce helium. If the pressure gauge PT01 reading increases, it indicates that the helium introduction was successful. If the introduction was successful, close the pneumatic valve AV01 after 10 seconds. Then open the vent valve AV09 and the vent valve AV08 to release the helium. If the PT01 reading is 0, it indicates that the venting was successful. Then close AV08 and AV09. b. Repeat steps a12-18 times to complete the helium replacement.

[0026] Preferably, the method for sample gas replacement in step 2 is as follows: c. Sample gas replacement: Open the pneumatic valve AV02 to introduce sample gas. If the pressure gauge PT01 reading increases, it indicates that the introduction of sample gas was successful. If the introduction was successful, close the pneumatic valve AV02 after 10 seconds, open the vent valve AV09, and then open the vent valve AV08 to discharge the sample gas. If the PT01 reading is 0, the venting was successful. Close AV08 and AV09. d. Repeat steps C3-5 times to complete the sample gas replacement; e. Normally open pneumatic valve AV02. Open pneumatic valve AV06 to allow sample gas to enter the moisture analyzer for analysis and detection. When the detected moisture content is less than 1 ppm, open AV03 to allow sample gas to enter the gas chromatograph for analysis and detection.

[0027] Preferably, the gas chromatograph analysis and detection method in step 3 is as follows: 1) At 0.01 minutes, pneumatic valve AV21 opens and AV22 closes. The sample gas enters the purge metering loop 1 and metering loop 2 from the seventh port and then exits from the twentieth port. 2) At 0.3 minutes, AV22 is turned on and AV21 is turned off. The sample gas is discharged through AV22. The first ten-way valve is switched to the quantitative loop 1 injection mode: the carrier gas 2 enters the backflush quantitative loop 1 from the fourth interface, enters the pre-column 1 from the ninth interface, and then enters the analytical column 1 through the third and second interfaces, and then enters the DID detector through the third interface of the four-way valve. 3) At 4 minutes, the 20th valve switches to the quantitative loop 2 injection mode: Carrier gas 3 enters the backflush quantitative loop 2 from the 19th port, enters the pre-column 2 from the 14th port, and then enters the analytical column 2 through the 17th and 18th ports; 4) At 5.5 minutes, the four-way valve switches to the column 2 injection mode, and the second port of the four-way valve is connected to the fourth port of the four-way valve to connect column 2 to the DID detector; 5) At 7.7 minutes, the four-way valve switches to the sample injection mode of the analysis column 1. The purpose is to cut off the chlorine gas in the analysis column 2 to the vent valve, so as to prevent chlorine gas from entering the DID detector and damaging the instrument. All valves are restored to their initial state before detection.

[0028] Among them, the pre-separation column 1 is a 5'×1 / 8'' silica gel column, which is corrosion-resistant and is used for pre-separation of H2, O2 / Ar, N2, CH4, and CO; the analytical column 1 is a 10'×1 / 8'' 13X Mol Sieve 1 / 8'' column, which is corrosion-resistant and is used to determine the contents of H2, O2 / Ar, N2, CH4, and CO in electronic-grade chlorine gas. The pre-separation column 2 is a 10'×1 / 8'' Hayesep D 1 / 8'' column, corrosion resistant, used for pre-separation of H2, O2 / Ar, N2, CH4, CO, CO2, and Cl2. The analytical column 2 is a 12'×1 / 8'' Hayesep Q 1 / 8'' column, corrosion resistant, used for determining the CO2 content in electronic-grade chlorine gas. The quantitative loop 1 is 1.0 mL, the quantitative loop 2 is 0.5 mL, the column oven temperature is 45℃, and the detector temperature is 23℃; the helium carrier gas flow rate is controlled at 30 mL / min by the flow controller MFC01.

[0029] The structural design features of this invention are as follows: 1. Four particulate filters are distributed in the analysis pipeline to ensure that the sample gas entering the moisture analyzer and gas chromatograph is free of particulate matter that could damage the instruments; 2. The analysis pipeline is equipped with manual metal diaphragm valves, pneumatic metal diaphragm valves, and manual ball valves. The pneumatic metal diaphragm valves are remotely controlled, while the manual metal diaphragm valves and manual ball valves are installed in the normally open pipeline upstream of the pneumatic metal diaphragm valves. 3. Ensure that the pipes and valves are resistant to chlorine corrosion. The metal material of the pipes and valves is Hastelloy, and the connection type is VCR connection. 4. To prevent exhaust gas backflow, a check valve should be installed on the exhaust gas pipeline; 5. Before injecting samples into the instrument, the tubing should be purged to ensure that the gas entering the tubing is free from interference; 6. N2 is an impurity component in gas chromatography analysis. To avoid interference with the analysis, the gas used to replace the gas chromatograph front-end pipeline should be helium. 7. To avoid damaging the gas chromatograph, the moisture content of the sample gas entering the gas chromatograph should be low. Therefore, the water content should be analyzed first before the sample is injected into the gas chromatograph. The sample should be injected into the gas chromatograph only after the water content of the water content is less than 1 ppm as indicated by the water analyzer. 8. Figure 1 AV06 and AV07 are equipped with valve interlocks to ensure that only one gas source enters the moisture analyzer at a time. 9. Figure 1 AV03, AV04 and AV05 are equipped with valve interlocks to ensure that only one gas source enters the gas chromatograph at a time. 10. Figure 1 AV01 and AV02 are equipped with valve interlocks to ensure that only one gas source enters the pipeline at a time. 11. To protect the instrument, the pressure gauge is set to alarm. When the pressure of PTO2 is higher than 1MPa or lower than 0.04MPa, an alarm will be triggered, and AV04 will be turned on to introduce helium into the gas chromatograph to protect the instrument. AV07 will be turned on to introduce nitrogen into the moisture analyzer to protect the instrument.

[0030] Example 1, as Figure 1 As shown: 1) Helium replacement: Open the pneumatic valve AV01 to introduce helium. If the pressure gauge PT01 reading increases, it indicates that the helium introduction was successful. If the introduction was successful, close the pneumatic valve AV01 after 10 seconds, open the vent valve AV09, and then open the vent valve AV08 to release the helium. If the PT01 reading is 0, it indicates that the venting was successful. Close AV08 and AV09. 2) Repeat step 1) 15 times to complete the helium replacement; 3) Sample gas replacement: Open the pneumatic valve AV02 to introduce sample gas. If the pressure gauge PT01 value increases, it indicates that the introduction of sample gas was successful. If the introduction is successful, close the pneumatic valve AV02 after 10 seconds, open the vent valve AV09 and then open the vent valve AV08 to discharge the sample gas. If the PT01 reading is 0, the venting is successful. Close AV08 and AV09. 4) Repeat step 3) to complete the sample gas replacement; 5) Normally open AV02 pneumatic valve, open pneumatic valve AV06 to allow sample gas to enter the moisture analyzer for analysis and detection.

[0031] Example 2: 1) When the moisture analyzer analysis result in step 5) of Example 1 is transmitted to the analysis panel and the moisture content is less than 1 ppm, turn on AV03 and the sample gas enters the gas chromatograph for analysis and detection. 2) At 0.01 minutes, pneumatic valve AV21 opens and AV22 closes. The sample gas enters the purge metering loop 1 and metering loop 2 from the first ten-way valve 7 interface and then exits from the second ten-way valve 10 interface. 3) At 0.3 minutes, AV22 turns on and AV21 turns off. The sample gas is discharged through AV22, and the first ten-way valve switches to the quantitative loop 1 injection mode: (e.g., ...) Figure 3 As shown, carrier gas 2 enters backflush metering loop 1 from port 4 of the first ten-way valve, enters pre-column 1 from port 9, then enters analytical column 1 through port 3 and port 2 of the first ten-way valve, and then enters DID detector through port 3 of the four-way valve. 4) At 4 minutes, the 20th valve switches to the quantitative loop 2 injection mode: (e.g., ...) Figure 4 As shown, carrier gas 3 enters backflush metering loop 2 from port 9 of the 20th port valve, enters pre-column 2 from port 4, and then enters analytical column 2 through ports 7 and 8 of the 20th port valve. 5) At 5.5 minutes, the four-way valve switches to the column 2 injection mode, and the four-way valve 2 interface is connected to interface 4 to connect the column 2 to the DID detector; 6) At 7.7 minutes, the four-way valve switches to the column 1 injection mode. The purpose is to cut off the chlorine gas in column 2 to the vent valve, so as to prevent chlorine gas from entering the DID detector and damaging the instrument. All valves are restored to their initial state before detection.

[0032] Figure 5 The peak times of the detected spectrum were 1.25 H2, 1.82 O2+Ar, 2.62 N2, 3.43 CH4, 4.55 CO, and 6.96 CO2.

[0033] The accuracy and stability of the method were evaluated using 10 consecutive parallel samples. The average recoveries of H2, O2+Ar, N2, CH4, CO, and CO2 in the 10 samples were 99.8%, 99.1%, 102.3%, 99.0%, 99.2%, and 94.5%, respectively. The RSDs of the results for the 10 parallel samples were 1.3, 1.3, 1.3, 1.1, 1.2, and 1.1, respectively, indicating that the method has good accuracy and stability. Compared with the national standard method (taking CH4 as an example), the significant differences between the two methods were compared using a paired-samples t-test. The results are shown in Table 1: t Calculated pass Count, here The average value represents the number of experiments in the method where n=10. d The standard deviation represents the difference.

[0034] t The result is 1.71, which is the critical value for two-tailed α=0.05 and df=9. t Value lookup table t 0.025,9 =2.26, which is less than the critical value, indicating that there is no significant difference between the two methods at a 95% confidence level.

[0035] The specific embodiments described herein are merely illustrative of the principles and effects of the invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in this invention should still be covered by the claims of this invention.

Claims

1. An automated electronic-grade liquid chlorine analysis system, comprising a moisture analyzer and a gas chromatograph, characterized in that: Both the moisture analyzer and the gas chromatograph are connected to the sample gas branch, nitrogen branch, and helium branch respectively via pipelines. A tail gas branch is also provided at the rear of the moisture analyzer, and multiple manual metal diaphragm valves and multiple pneumatic metal diaphragm valves are installed on the pipeline.

2. The automated electronic-grade liquid chlorine analysis system according to claim 1, characterized in that: The sample gas in the sample gas branch enters through the manual metal diaphragm valve MV01 and the pneumatic metal diaphragm valve AV02, then enters the gas chromatograph through the pneumatic metal diaphragm valve AV03, enters the moisture analyzer through the pneumatic metal diaphragm valve AV06, and is discharged to the tail gas branch through the pneumatic metal diaphragm valve AV08.

3. The automated electronic-grade liquid chlorine analysis system according to claim 1, characterized in that: Helium in the helium branch enters through manual metal diaphragm valve MV10, manual metal diaphragm valve MV02 and pneumatic metal diaphragm valve AV01, and is then discharged to the tail gas branch through pneumatic metal diaphragm valve AV08; after entering through manual metal diaphragm valve MV11 and manual metal diaphragm valve MV04, it is divided into two paths, one of which enters the gas chromatograph through MV03 as carrier gas and driving gas, and the other of which enters the gas chromatograph through AV04 as protective gas.

4. The automated electronic-grade liquid chlorine analysis system according to claim 1, characterized in that: The nitrogen in the nitrogen branch enters through manual metal diaphragm valves MV13 and MV08, and then enters the moisture meter as a protective gas through pneumatic metal diaphragm valve AV07.

5. The automated electronic-grade liquid chlorine analysis system according to claim 1, characterized in that: The gas chromatograph includes two 10-port valves and one 4-port valve, two quantitative loops, one DID detector, and four chromatographic columns. The seventh port of the first 10-port valve is the sample gas inlet, connected to the eighth port. A first quantitative loop 1 is located between the eighth and fifth ports. The fifth port is connected to the sixth port, and the sixth port is connected to the twelfth port of the second 10-port valve. The fourth port is the carrier gas 2 inlet, connected to the third port. A pre-separation column 1 is located between the third and ninth ports. The ninth port is connected to the tenth port, which is also a vent. The first port is the carrier gas 1 inlet, connected to the second port. An analytical column 1 is located between the second port and the third port of the 4-port valve. The third port of the 4-port valve is connected to the fourth port, and the fourth port of the 4-port valve is connected to the DID detector.

6. The automated electronic-grade liquid chlorine analysis system according to claim 1, characterized in that: The twelfth and thirteenth ports of the second ten-way valve are connected, and a second quantitative ring 2 is provided between the thirteenth and twentieth ports. The twentieth port is connected to the eleventh port. The nineteenth port is the inlet of the carrier gas 3 and is connected to the eighteenth port. The pre-separation column 2 is located between the eighteenth and fourteenth ports. The fourteenth port is connected to the fifteenth port. Both the eleventh and fifteenth ports are vent ports. The sixteenth port is the inlet of the carrier gas 4 and is connected to the seventeenth port. The analysis column 2 is located between the seventeenth port and the second port of the four-way valve. The second port of the four-way valve is connected to the first port of the four-way valve, which is also a vent port.

7. The method of using the electronic-grade liquid chlorine automated analysis system according to any one of claims 1-6, characterized in that: The method includes the following steps:

1. Pretreatment: The internal gas is purged by helium purging, and then sample gas is introduced; 2. After the sample gas is introduced, all the helium is purged to replace the helium with the sample gas. After the replacement is completed, the moisture analyzer is turned on to detect the moisture content.

3. After the moisture content is detected, the sample is analyzed by gas chromatography for final determination.

8. The method of using the electronic-grade liquid chlorine automated analysis system according to claim 1, characterized in that: The preprocessing method in step 1 is as follows: a. Open the pneumatic valve AV01 to introduce helium. If the pressure gauge PT01 reading increases, it indicates that the helium introduction was successful. If the introduction was successful, close the pneumatic valve AV01 after 10 seconds. Then open the vent valve AV09 and the vent valve AV08 to release the helium. If the PT01 reading is 0, it indicates that the venting was successful. Then close AV08 and AV09. b. Repeat steps a12-18 times to complete the helium replacement.

9. The method of using the electronic-grade liquid chlorine automated analysis system according to claim 1, characterized in that: The method for sample gas replacement in step 2 is as follows: c. Sample gas replacement: Open the pneumatic valve AV02 to introduce sample gas. If the pressure gauge PT01 reading increases, it indicates that the introduction of sample gas was successful. If the introduction was successful, close the pneumatic valve AV02 after 10 seconds, open the vent valve AV09, and then open the vent valve AV08 to discharge the sample gas. If the PT01 reading is 0, the venting was successful. Close AV08 and AV09. d. Repeat steps C3-5 times to complete the sample gas replacement; e. Normally open pneumatic valve AV02. Open pneumatic valve AV06 to allow sample gas to enter the moisture analyzer for analysis and detection. When the detected moisture content is less than 1 ppm, open AV03 to allow sample gas to enter the gas chromatograph for analysis and detection.

10. The method of using the electronic-grade liquid chlorine automated analysis system according to claim 1, characterized in that: The gas chromatography analysis and detection method in step 3 is as follows: 1) At 0.01 minutes, pneumatic valve AV21 opens and AV22 closes. The sample gas enters the purge metering loop 1 and metering loop 2 from the seventh port and then exits from the twentieth port. 2) At 0.3 minutes, AV22 is turned on and AV21 is turned off. The sample gas is discharged through AV22. The first ten-way valve is switched to the quantitative loop 1 injection mode: the carrier gas 2 enters the backflush quantitative loop 1 from the fourth interface, enters the pre-column 1 from the ninth interface, and then enters the analytical column 1 through the third and second interfaces, and then enters the DID detector through the third interface of the four-way valve. 3) At 4 minutes, the 20th valve switches to the quantitative loop 2 injection mode: Carrier gas 3 enters the backflush quantitative loop 2 from the 19th port, enters the pre-column 2 from the 14th port, and then enters the analytical column 2 through the 17th and 18th ports; 4) At 5.5 minutes, the four-way valve switches to the column 2 injection mode, and the second port of the four-way valve is connected to the fourth port of the four-way valve to connect column 2 to the DID detector; 5) At 7.7 minutes, the four-way valve switches to the sample injection mode of the analysis column 1. The purpose is to cut off the chlorine gas in the analysis column 2 to the vent valve, so as to prevent chlorine gas from entering the DID detector and damaging the instrument. All valves are restored to their initial state before detection.

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