A gas pyrolysis pretreatment system for total halide detection in hydrogen energy

Abstract

The utility model relates to hydrogen energy fuel technology field, concretely is a kind of gas pyrolysis pretreatment system for total halide detection in hydrogen energy, including gas cylinder, pyrolysis furnace and ion chromatograph and several connecting gas cylinder, pyrolysis furnace and ion chromatograph's pipeline, the inside storage of gas cylinder has the gas to be measured, the outer surface of pyrolysis furnace is fixedly installed with installation shell, the side of installation shell is installed with air inlet end, water inlet end and sample outlet, and the front of installation shell is provided with pyrolysis furnace switch, temperature rising starting switch, heating display lamp and temperature control panel. The gas pyrolysis pretreatment system for total halide detection in hydrogen energy, by high-temperature pyrolysis organic halide, can solve the problem that hydrogen flame combustion detector cannot burn part halide, convert organic halide of multiple halogen atom number into inorganic halide completely, after total inorganic halide after high-temperature pyrolysis condenses, into absorption liquid secondary absorption, further increase conversion efficiency.

Description

Technical Field

[0001] This utility model relates to the field of hydrogen fuel technology, specifically to a high-temperature gas cracking pretreatment system for detecting total halides in hydrogen energy. Background Technology

[0002] Hydrogen has garnered significant attention for its use in hydrogen fuel cells, power generation, and energy storage. Hydrogen primarily originates from industrial byproducts, water electrolysis, coal production, and petroleum cracking. These processes introduce various gaseous impurities, among which halides are particularly concerning. Their presence can poison platinum catalysts and inhibit ion transport within membranes, thus affecting the conversion of chemical energy into electrical energy. Excessive halides can also lower the calorific value, impacting the combustion efficiency of hydrogen fuels.

[0003] Halides in hydrogen gas are generally hydrogen halides (HX) and organohalides (RX). Internationally and domestically, the detection of organohalides in hydrogen gas commonly uses gas chromatography / mass spectrometry (GC / MS), or gas chromatography (GC) equipped with flame ionization detectors (FID), helium discharge ionization detectors (DID), and enhanced plasma discharge detectors (EPD). The detection limit of GC / MS in selected ion mode can reach 10 ppb, but this mode is only suitable for the detection of known organohalides; the detection limit for unknown halides is above 0.1 ppm. In gas chromatography equipped with various detectors, the FID detector cannot detect non-flammable organohalides, and its detection limit is above 0.1 ppm. General-purpose sensitive detectors such as DID, PDHID, and EPD have detection limits of around 1-100 ppb, but they have significant limitations, cannot qualitatively identify unknown organohalides, and require high-performance chromatographic columns for separating various organohalides. Besides the qualitative issues, another difficult problem to solve with both GC / MS and GC methods is the inability to accurately quantify all organohalides. This is because the most commonly used comparative methods in gas detection require the use of standard substances to calibrate the samples, and the large variety of organohalides makes obtaining standard substances extremely difficult. For the detection of inorganic halides in hydrogen, they are transferred from the gas phase to the liquid phase via an absorption device, and then detected using ion chromatography. However, ion chromatography is limited in that it cannot detect organohalides. In other words, organic and inorganic halides in gases are tested using completely different measurement methods; the two cannot be combined or substituted, and many problems such as qualitative and quantitative issues exist. Utility Model Content

[0004] The purpose of this invention is to provide a high-temperature gas cracking pretreatment system for detecting total halides in hydrogen energy, in order to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, this utility model provides the following technical solution:

[0006] A high-temperature gas pyrolysis pretreatment system for detecting total halides in hydrogen energy includes a gas cylinder, a pyrolysis furnace, an ion chromatograph, and several pipes connecting the gas cylinder, the pyrolysis furnace, and the ion chromatograph. The gas cylinder stores the gas to be tested. A mounting shell is fixedly installed on the outer surface of the pyrolysis furnace. An inlet, a water inlet, and a sample outlet are installed on the side of the mounting shell. A pyrolysis furnace switch, a temperature start switch, a heating indicator light, and a temperature control panel are provided on the front of the mounting shell. The pyrolysis furnace switch, temperature start switch, heating indicator light, and temperature control panel are all electrically connected to the pyrolysis furnace. A storage cavity is opened on the front of the ion chromatograph, and the gas cylinder is installed inside the storage cavity. An upper mounting slot and a lower mounting slot are opened on the back of the ion chromatograph. A water storage bottle, valve one, valve two, valve three, an absorption column, a water pump one, and a water pump two are installed inside the upper mounting slot. A high-pressure infusion pump one, a six-way valve, a high-pressure infusion pump two, an eluent generator, a chromatographic column, an inhibitor, and a detector are installed inside the lower mounting slot.

[0007] The gas cylinder is connected to the gas inlet end via an ion chromatograph to control the flow rate. The inside of the gas inlet end is connected to the input end of the pyrolysis furnace to introduce a set amount of the gas to be tested into the pyrolysis furnace. One end of the water inlet end is connected to a water storage bottle via a high-pressure infusion pump, and the other end of the water inlet end is connected to the pyrolysis furnace to pump ultrapure water into the pyrolysis furnace.

[0008] A condenser is installed at the output port of the pyrolysis furnace, and the condenser is connected to the ion chromatograph through the sample outlet.

[0009] The six-way valve is equipped with six-way valve port 1, six-way valve port 2, six-way valve port 3, six-way valve port 4, six-way valve port 5 and six-way valve port 6. Six-way valve port 1 is connected to the eluent generator, six-way valve port 2 is connected to the chromatographic column, six-way valve port 4 is connected to valve port 3, six-way valve port 5 is connected to water pump 2, and a metering loop is connected between six-way valve port 3 and six-way valve port 6.

[0010] The quantitative loop is connected to the eluent generator via a six-way valve. The eluent generator is connected to the water storage bottle. A high-pressure pump is installed on the pipeline between the water storage bottle and the eluent generator to pump ultrapure water into the eluent generator. The eluent generator converts the ultrapure water into eluent and carries the sample through the chromatographic column, the suppressor and the detector in sequence.

[0011] The absorption column is connected to the sample outlet through valve one and valve two. The input end of the water pump one is connected to the water storage bottle, and the output end of the water pump one is connected to the absorption column. The absorption column is connected to the four ports of the six-way valve through valve three.

[0012] Preferably, the temperature control panel is used to set and adjust the temperature of the pyrolysis furnace, with the set temperature range being room temperature to 1000°C.

[0013] Preferably, an exhaust pipe is fixedly installed on the upper surface of the ion chromatograph, and the bottom end of the exhaust pipe is connected to the absorption column for discharging hydrogen gas.

[0014] Preferably, valve one, valve two, and valve three are all solenoid valves.

[0015] Preferably, a fan is provided on the mounting housing, and the fan's air outlet corresponds to the condenser pipe.

[0016] Preferably, pump one provides ultrapure water to the absorption column for secondary absorption of incompletely dissolved halides; pump two is used to transfer the sample from the absorption column to the quantitative loop.

[0017] Compared with the prior art, this utility model provides a gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy, which has the following beneficial effects:

[0018] 1. This gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy can solve the problem that hydrogen flame combustion detectors cannot burn some halides by pyrolyzing organic halides at high temperatures, and completely converts organic halides with multiple halogen atoms into inorganic halides.

[0019] 2. The gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy condenses the total inorganic halides after high-temperature pyrolysis and then enters the absorbent for secondary absorption, further increasing the conversion efficiency.

[0020] 3. This high-temperature gas pyrolysis pretreatment system for detecting total halides in hydrogen does not use any other auxiliary gases, only sample hydrogen, and will not introduce additional pollution.

[0021] 4. The high-temperature gas pyrolysis pretreatment system for detecting total halides in hydrogen energy converts all organic and inorganic halides in the gas to be tested into inorganic halides before entering the detection system, reducing the greater consumption caused by separate sample testing and improving testing efficiency. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the structure of this utility model;

[0023] Figure 2 This is a schematic diagram of the structure of this utility model from another angle;

[0024] Figure 3 for Figure 2 Enlarged view of the structure at point A in the middle;

[0025] Figure 4 for Figure 2 Enlarged view of the structure at point B in the middle.

[0026] In the diagram: 1. Pyrolysis furnace switch; 2. Heating start switch; 3. Heating indicator light; 4. Temperature control panel; 5. Gas cylinder; 6. Gas inlet; 7. Water inlet; 8. Sample outlet; 9. Condenser; 10. High-pressure infusion pump one; 11. Water storage bottle; 12. Valve one; 13. Valve two; 14. Valve three; 15. Absorption column; 16. Water pump one; 17. Water pump two; 18. Quantitative loop; 19. High-pressure infusion pump two; 20. Eluent generator; 21. Chromatographic column; 22. Suppressor; 23. Detector; 24. Pyrolysis furnace; 25. Ion chromatograph; 26. Fan; 181. Six-way valve port one; 182. Six-way valve port two; 183. Six-way valve port three; 184. Six-way valve port four; 185. Six-way valve port five; 186. Six-way valve port six. Detailed Implementation

[0027] Please see Figure 1-4 A high-temperature gas pyrolysis pretreatment system for detecting total halides in hydrogen energy includes a gas cylinder 5, a pyrolysis furnace 24, an ion chromatograph 25, and several pipes connecting the gas cylinder 5, the pyrolysis furnace 24, and the ion chromatograph 25. The gas cylinder 5 stores the gas to be tested. The ion chromatograph 25 has a storage cavity on its front, and the gas cylinder 5 is installed inside the storage cavity. The ion chromatograph 25 has an upper mounting slot and a lower mounting slot on its back. The upper mounting slot is equipped with a water storage bottle 11, valve one 12, valve two 13, valve three 14, an absorption column 15, a water pump one 16, and a water pump two 17, forming an integrated module for sample collection and transfer. The lower mounting slot is equipped with a high-pressure infusion pump one 10, a quantitative loop 18, a high-pressure infusion pump two 19, an eluent generator 20, a chromatographic column 21, an inhibitor 22, and a detector 23, forming an integrated module for sample separation and detection.

[0028] A mounting shell is fixedly installed on the outer surface of the pyrolysis furnace 24. An inlet 6, a water inlet 7, and a sample outlet 8 are installed on the side of the mounting shell. A pyrolysis furnace switch 1, a temperature start switch 2, a heating indicator light 3, and a temperature control panel 4 are located on the front of the mounting shell. All four switches are electrically connected to the pyrolysis furnace 24. A gas cylinder 5 is connected to the inlet 6 via an ion chromatograph 25, controlling its flow rate. The inner side of the inlet 6 is connected to the input end of the pyrolysis furnace 24, used to introduce a set amount of the gas to be tested into the pyrolysis furnace 24. One end of the water inlet 7 is connected to a water storage bottle 11 via a high-pressure infusion pump 10, and the other end is connected to the pyrolysis furnace 24, pumping ultrapure water into the pyrolysis furnace. A condenser tube 9 is installed at the output port of the pyrolysis furnace 24, and the condenser tube 9 is connected to the ion chromatograph 25 via the sample outlet 8.

[0029] When the device is in operation, the pyrolysis furnace is first turned on, and the temperature is set to 950℃ via the temperature control panel. After the temperature stabilizes, the hydrogen gas to be tested enters the pyrolysis furnace through the gas inlet 6. At the same time, the high-pressure liquid pump 10 pumps a fixed amount of ultrapure water through the water inlet 7. Under high temperature conditions, the molecular bonds of the organic halides (RX) in the hydrogen gas break, and in the presence of water vapor, they are reduced by hydrogen gas to generate the corresponding inorganic halides (HX), while the originally present inorganic halides (HX) remain unchanged. This step achieves the uniform conversion of all forms of halides into halide ions (X-). The high-temperature gas mixture after the reaction is rapidly cooled in the condenser 9, and the water vapor condenses into liquid water, in which the halide ions dissolve to form a solution containing halide ions.

[0030] The six-way valve is equipped with a six-way valve port 181, a six-way valve port 282, a six-way valve port 383, a six-way valve port 484, a six-way valve port 585, and a six-way valve port 686. The six-way valve port 181 is connected to the eluent generator 20, the six-way valve port 282 is connected to the chromatographic column 21, the six-way valve port 484 is connected to the valve 3 14, and the six-way valve port 585 is connected to the water pump 2 17. A metering loop 18 is connected between the six-way valve port 383 and the six-way valve port 686.

[0031] The quantitative loop 18 is connected to the eluent generator 20 via a six-way valve. The eluent generator 20 is connected to the water storage bottle 11. A high-pressure infusion pump 19 is installed on the pipeline between the water storage bottle 11 and the eluent generator 20, pumping ultrapure water into the eluent generator 20. The eluent generator 20 converts the ultrapure water into eluent and carries the sample sequentially through the chromatographic column 21, the suppressor 22, and the detector 23. A water pump 16 provides ultrapure water to the absorption column 15 for secondary absorption of incompletely dissolved halides. A water pump 17 is used to transfer the sample from the absorption column 15 to the quantitative loop 18. The eluent generator 20 converts the ultrapure water into KOH eluent online.

[0032] By opening valve 3 (14) and starting pump 2 (17), the sample solution in the absorption column is quantitatively transferred to the quantitative loop (18). Then, the flow path is switched via a six-way valve, and the KOH eluent generated by high-pressure pump 2 (19) and eluent generator 20 carries the sample from the quantitative loop into the chromatographic column 21. Different types of halide ions (such as F-, Cl-, Br-) are then eluented. - The compounds are separated in the chromatographic column due to different retention times and then enter the suppressor 22 and detector 23 in sequence, ultimately achieving qualitative and quantitative analysis of total halides.

[0033] The absorption column 15 is connected to the sample outlet 8 through valve 12 and valve 23. The input end of the water pump 16 is connected to the water storage bottle 11, and the output end of the water pump 16 is connected to the absorption column 15. The absorption column 15 is connected to the four-port 184 of the six-way valve through valve 3. In the absorption column, the ultrapure water provided by the water pump 16 performs secondary absorption on any halide that may remain in the gas phase, ensuring complete capture.

[0034] Furthermore, the temperature control panel 4 is used to set and adjust the temperature of the pyrolysis furnace, with the set temperature range being room temperature to 1000°C, preferably set to 950°C.

[0035] Furthermore, an exhaust pipe is fixedly installed on the upper surface of the ion chromatograph 15, and the bottom end of the exhaust pipe is connected to the absorption column 15 for safely discharging the hydrogen gas generated in the reaction.

[0036] Furthermore, valves 12, 13, and 14 are all solenoid valves. The pyrolysis furnace 24 and ion chromatograph 25 are electrically connected to the laboratory computer. By setting a program in the computer, the opening and closing of valves 12, 13, and 14, the flow rate of high-pressure infusion pumps 10 and 29, and the start and stop of water pumps 16 and 217 are automatically controlled, which is convenient for staff to operate.

[0037] Working principle: This high-temperature gas cracking pretreatment system for detecting total halides in hydrogen energy first turns on the cracking furnace and sets the temperature to 950°C via the temperature control panel. After the temperature stabilizes, the hydrogen gas to be tested enters the cracking furnace through the gas inlet (6). At the same time, the high-pressure liquid pump (10) pumps a certain amount of ultrapure water through the water inlet (7). Under high temperature conditions, the molecular bonds of organic halides (RX) in hydrogen break, and under the condition of water vapor, they are reduced by hydrogen to generate the corresponding inorganic halides (HX), while the inorganic halides (HX) that were originally present remain unchanged. This step realizes the unified conversion of all forms of halides into halide ions (X-).

[0038] The high-temperature gas mixture after the reaction is rapidly cooled in the condenser (9), and the water vapor is condensed into liquid water, which dissolves the halide ions to form a solution containing halide ions. This solution enters the absorption column (15) of the ion chromatograph under pressure.

[0039] In the absorption column, ultrapure water supplied by pump 1 (16) is used to perform secondary absorption of any halides that may remain in the gas phase, ensuring complete capture. Meanwhile, excess hydrogen is safely discharged from the system through the vent at the top of the absorption column.

[0040] Through program control, valve three (14) is opened and water pump two (17) is started, quantitatively transferring the sample solution in the absorption column to the quantitative loop (18). Subsequently, the system automatically switches the flow path, and the KOH eluent generated by high-pressure pump two (19) and eluent generator (20) carries the sample in the quantitative loop into the chromatographic column (21). Different types of halide ions (such as F-, Cl-, Br-) are separated. - The compounds are separated in the chromatographic column due to different retention times and enter the suppressor (22) and detector (23) in sequence, thus achieving qualitative and quantitative analysis of total halides.

Claims

1. A gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy, comprising a gas cylinder (5), a pyrolysis furnace (24), and an ion chromatograph (25), and several pipes connecting the gas cylinder (5), the pyrolysis furnace (24), and the ion chromatograph (25), wherein the gas cylinder (5) stores the gas to be tested, characterized in that: A mounting shell is fixedly installed on the outer surface of the pyrolysis furnace (24). An air inlet (6), a water inlet (7), and a sample outlet (8) are installed on the side of the mounting shell. A pyrolysis furnace switch (1), a temperature start switch (2), a heating indicator light (3), and a temperature control panel (4) are provided on the front of the mounting shell. The pyrolysis furnace switch (1), temperature start switch (2), heating indicator light (3), and temperature control panel (4) are all electrically connected to the pyrolysis furnace (24). A storage cavity is opened on the front of the ion chromatograph (25). The gas cylinder (5) Installed inside the storage chamber, the ion chromatograph (25) has an upper mounting slot and a lower mounting slot on its back. The upper mounting slot is equipped with a water storage bottle (11), valve one (12), valve two (13), valve three (14), absorption column (15), water pump one (16), and water pump two (17). The lower mounting slot is equipped with a high-pressure infusion pump one (10), a six-way valve, a high-pressure infusion pump two (19), an eluent generator (20), a chromatographic column (21), an inhibitor (22), and a detector (23). The gas cylinder (5) is connected to the gas inlet (6) by controlling the flow rate through the ion chromatograph (25). The inside of the gas inlet (6) is connected to the input end of the pyrolysis furnace (24) for introducing a set amount of gas to be tested into the pyrolysis furnace (24). One end of the water inlet (7) is connected to the water storage bottle (11) through the high-pressure infusion pump (10), and the other end of the water inlet (7) is connected to the pyrolysis furnace (24). A condenser tube (9) is installed at the output port of the pyrolysis furnace (24), and the condenser tube (9) is connected to the ion chromatograph (25) through the sample outlet (8); The six-way valve is provided with a six-way valve port 1 (181), a six-way valve port 2 (182), a six-way valve port 3 (183), a six-way valve port 4 (184), a six-way valve port 5 (185), and a six-way valve port 6 (186). The six-way valve port 1 (181) is connected to the eluent generator (20), the six-way valve port 2 (182) is connected to the chromatographic column (21), the six-way valve port 4 (184) is connected to the valve 3 (14), the six-way valve port 5 (185) is connected to the water pump 2 (17), and a metering loop (18) is connected between the six-way valve port 3 (183) and the six-way valve port 6 (186). The quantitative loop (18) is connected to the eluent generator (20) via a six-way valve. The eluent generator (20) is connected to the water storage bottle (11). The high-pressure infusion pump (19) is installed on the pipeline between the water storage bottle (11) and the eluent generator (20) to pump ultrapure water into the eluent generator (20). The eluent generator (20) converts ultrapure water into eluent and drives the sample to flow sequentially through the chromatographic column (21), the suppressor (22), and the detector (23). The absorption column (15) is connected to the sample outlet (8) through the valve one (12) and the valve two (13). The input end of the water pump one (16) is connected to the water storage bottle (11). The output end of the water pump one (16) is connected to the absorption column (15). The absorption column (15) is connected to the four ports of the six-way valve (184) through the valve three (14).

2. The gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy according to claim 1, characterized in that: The temperature control panel (4) is used to set and adjust the temperature of the pyrolysis furnace, with the set temperature range being room temperature to 1000℃.

3. The gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy according to claim 1, characterized in that: An exhaust pipe is fixedly installed on the upper surface of the ion chromatograph (25), and the bottom end of the exhaust pipe is connected to the absorption column (15) for discharging hydrogen gas.

4. The gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy according to claim 1, characterized in that: Valve 1 (12), Valve 2 (13), and Valve 3 (14) are all solenoid valves.

5. The gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy according to claim 1, characterized in that: A fan (26) is provided on the mounting housing, and the air outlet of the fan (26) corresponds to the condenser pipe (9).

6. The gas high-temperature pyrolysis pretreatment system for detecting total halides in hydrogen energy according to claim 1, characterized in that: The first water pump (16) provides ultrapure water to the absorption column (15) for secondary absorption of incompletely dissolved halides; the second water pump (17) is used to transfer the sample from the absorption column (15) to the quantitative loop (18).

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