CN113960217A - Method and system for measuring content of gas components in fuel hydrogen - Google Patents
Method and system for measuring content of gas components in fuel hydrogen Download PDFInfo
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- CN113960217A CN113960217A CN202111396017.XA CN202111396017A CN113960217A CN 113960217 A CN113960217 A CN 113960217A CN 202111396017 A CN202111396017 A CN 202111396017A CN 113960217 A CN113960217 A CN 113960217A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
- G01N30/461—Flow patterns using more than one column with serial coupling of separation columns
- G01N30/463—Flow patterns using more than one column with serial coupling of separation columns for multidimensional chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
Abstract
The invention discloses a method and a system for measuring the content of gas components in fuel hydrogen. When nitrogen gas separates from first chromatographic column, first chromatographic column switches to and communicates with second chromatographic column, carries nitrogen gas methane carbon monoxide to second chromatographic column, measures its content by the helium ionization detector of pulse discharge, not only can avoid once only separating gas sample, and fuel hydrogen content is high, causes easily that the permanent gas that will separate out breaks away from first chromatographic column, causes the inaccuracy of testing result, and divide twice completion to improve detection efficiency as far as, avoids the separation time extension.
Description
Technical Field
The invention relates to the technical field of gas chromatography analysis, in particular to a method and a system for measuring the content of gas components in fuel hydrogen.
Background
The current water content is determined by the method specified in Chapter 6 GB/T5832.2 or Chapter 6 GB/T5832.3, total hydrocarbons (as CH)4Gauge) of the content is determined according to the method specified in chapter 7 of GB/T8984, the oxygen content is determined according to the method specified in chapter 6 of GB/T6285 (trace oxygen is measured by an electrochemical method) or chapter 7 of GB/T5831 (trace oxygen is measured by an electrochemical method), the nitrogen and argon content is determined according to the method specified in chapter 5 of GB/T3634.2, the carbon dioxide content is determined according to the method specified in chapter 7 of GB/T8984, the carbon monoxide content is determined according to the method specified in chapter 7 of GB/T8984 or chapter 5 of GB/T9801 (non-dispersive infrared method), the formaldehyde content is determined according to the method specified in chapter 6 of GB/T16129 (by a spectroscopic method), and the ammonia content is determined according to the method specified in chapter 6 of GB/T14669 (method for ion selective electrodes). The content of each component is determined by adopting different methods, and in order to separate each component, a plurality of analysis methods are adopted to be matched and combined, so that the analysis and detection are complex.
Patent document CN101887051A discloses an on-line chromatographic analysis method, which adopts the technical scheme of two serially connected analysis systems, one of which is a hydrogen/permanent gas analysis system, and the other is a non-aromatic and aromatic hydrocarbon analysis system, so as to better solve the problem of simultaneous analysis of hydrogen/permanent gas, non-aromatic and aromatic hydrocarbon mixtures and the problem of water interference during analysis, and can be used for on-line chromatographic analysis of water-containing, hydrogen/permanent gas, non-aromatic and aromatic hydrocarbon mixtures. The patent document CN106153431A discloses a detection method and a device for rapidly determining components of crude gas, and the invention discloses a detection method and a device for rapidly determining components of crude gas, which mainly solve the problems of non-linearity of carbon dioxide determination, high TCD detection limit, high cost of a multi-color spectral column measurement system, long detection time and the like in the prior art of crude gas chromatography. The device for rapidly measuring the components of the crude gas mainly comprises a purification device, a chromatographic column separation device, a conversion device, a detector and a data processing unit, wherein the purification device is used for dedusting, desulfurizing and dehydrating the crude gas; the multi-color column separation device is used for separating each gas component; the conversion device converts carbon dioxide and carbon monoxide into methane; the detector and the data processing unit are used for qualitative and quantitative analysis, but in the above two patent documents, a single chromatographic column is used for separation of permanent gas, and gas except the permanent gas is retained by the single chromatographic column, which inevitably causes inaccurate measurement and complicated chromatographic column structure.
Disclosure of Invention
The invention aims to provide a method and a system for measuring the content of a gas component in fuel hydrogen, which are used for solving the problems in the prior art, a first quantitative ring is used for quantifying the gas sample, a first chromatographic column is used for separating permanent gas, the quantified gas sample is evacuated through the first chromatographic column twice, the situation that the hydrogen component in the fuel hydrogen is evacuated once is avoided, the permanent gas is separated from the first chromatographic column due to excessive content of the hydrogen component, the subsequent measurement process of the permanent gas is inaccurate, a second chromatographic column is arranged for further separating the permanent gas, the separation degree of the permanent gas is improved, and the detection accuracy of the permanent gas is ensured.
In order to achieve the purpose, the invention provides the following scheme: the invention provides a method for measuring the content of gas components in fuel hydrogen, which comprises the following steps of:
sampling: preparing a retention passage, wherein the retention passage is provided with a first quantitative ring, introducing a gas sample into the retention passage, and quantitatively sampling the gas sample through the first quantitative ring;
the main component before hydrogen is discharged by the first exhaust valve, when the first chromatographic column of oxygen argon is separated, the first chromatographic column is communicated with the second chromatographic column, the oxygen argon is carried into the second chromatographic column, when the oxygen argon completely enters the second chromatographic column, the first chromatographic column is switched to be communicated with the first exhaust valve, and the main component after hydrogen is discharged. When the nitrogen is separated from the first chromatographic column, the first chromatographic column is switched to be communicated with the second chromatographic column, the nitrogen, methane and carbon monoxide are carried to the second chromatographic column, and the content of the nitrogen, methane and carbon monoxide is measured by a pulse discharge helium ionization detector.
Preferably, a second chromatographic column is arranged on the detection passage, the first carrier gas carries the permanent gas in the first chromatographic column into the second chromatographic column, and the second chromatographic column separates the permanent gas.
Preferably, the method comprises the following system sampling process before the detection of the permanent gas:
a gas sample sequentially flows through a first quantitative ring, a second quantitative ring and a third quantitative ring through a gas sample inlet and then enters a dew point transmitter, and the first quantitative ring, the second quantitative ring and the third quantitative ring quantitatively measure the gas sample sequentially;
and the gas sample enters the temperature-changing concentration desorber through the gas sample inlet, and the gas sample is concentrated by the temperature-changing concentration desorber and then filled in the sample storage passage.
Preferably, a water content determination process is included after the system sampling process:
as the gas sample flows to the dew point transmitter, the moisture in the gas sample is read directly by the dew point transmitter.
Preferably, a capnometry process is included after the system sampling process:
and the second carrier gas carries the gas sample in the second quantitative ring to enter a third chromatographic column, the third chromatographic column intercepts carbon dioxide, the rest gas enters a second exhaust valve to be exhausted, the communication between the third chromatographic column and the second exhaust valve is cut off, the second carrier gas carries the carbon dioxide in the third chromatographic column to enter a pulse discharge helium ionization detector, and the content of the carbon dioxide is measured by the pulse discharge helium ionization detector.
Preferably, an argon, oxygen determination process is included after the system sampling process:
and the third carrier gas carries the gas sample in the third quantitative ring to enter a fourth chromatographic column, the fourth chromatographic column intercepts argon and oxygen, the rest gas enters a third exhaust valve to be exhausted, the communication between the fourth chromatographic column and the third exhaust valve is cut off, the third carrier gas carries the argon and the oxygen separated from the fourth chromatographic column to enter a fifth chromatographic column, the argon and the oxygen are separated again through the fifth chromatographic column and then enter a pulse discharge helium ionization detector, and the content of the argon and the content of the oxygen are measured through the pulse discharge helium ionization detector.
Preferably, the method comprises the following ammonia and formaldehyde determination processes after the system sampling process:
and the fourth carrier gas carries the concentrated gas sample in the sample storage passage to enter a sixth chromatographic column, the sixth chromatographic column intercepts ammonia and formaldehyde, the rest gas enters a fourth exhaust valve to be exhausted, before the ammonia and the formaldehyde flow out of the sixth chromatographic column, the communication between the sixth chromatographic column and the fourth exhaust valve is cut off, the fifth carrier gas carries the ammonia and the formaldehyde intercepted by the sixth chromatographic column to enter a seventh chromatographic column, the seventh chromatographic column further separates the ammonia and the formaldehyde, the separated ammonia and the formaldehyde enter a pulse discharge helium ionization detector, and the content of the ammonia and the formaldehyde is measured by the pulse discharge helium ionization detector.
Also provides a system for measuring the content of the gas component in the fuel hydrogen, which comprises a permanent gas content measuring device, the permanent gas content measuring device comprises a retention passage, a first quantitative ring and a first chromatographic column are arranged in the retention passage, the first quantitative ring and the first chromatographic column are sequentially arranged along the gas flowing direction, the outlet of the first chromatographic column is communicated with a multi-way switching valve, the multi-way switching valve is communicated with a detection passage and a first exhaust valve, the detection passage is provided with a pulse discharge helium ionization detector, the first exhaust valve and the pulse discharge helium ionization detector are respectively communicated with the first chromatographic column through the multi-way switching valve in an alternating way, and a second chromatographic column is arranged on the detection channel and communicated between the pulse discharge helium ionization detector and the multi-way switching valve.
Preferably, the multi-way switching valve is a first automatic switching six-way valve, the first automatic switching six-way valve is communicated with the first exhaust valve, an outlet of the first chromatographic column and an inlet of the second chromatographic column, the first automatic switching six-way valve is connected with a first automatic switching ten-way valve, the first automatic switching ten-way valve is communicated with a gas sample inlet and an inlet of the first quantitative ring, and the first automatic switching ten-way valve is communicated with a first carrier gas used for bringing the gas sample in the first quantitative ring into the first chromatographic column.
Preferably, the apparatus further comprises a carbon dioxide content measuring device configured to match with the permanent gas content measuring device, the carbon dioxide content measuring device comprises a second quantitative ring communicated with a first automatic switching ten-way valve, the first automatic switching ten-way valve is communicated with a third chromatographic column for separating carbon dioxide, the first automatic switching ten-way valve is communicated with a second carrier gas for bringing a gas sample in the second quantitative ring into the third chromatographic column, the third chromatographic column is connected with a second automatic switching six-way valve, the second automatic switching six-way valve is communicated with a second vent valve and a pulse discharge helium ionization detector, the second vent valve and the pulse discharge helium ionization detector are respectively and alternately communicated with the third chromatographic column, and the pulse discharge ionization detector is communicated with the second automatic switching six-way valve;
the argon-oxygen content measuring device comprises a first automatic switching ten-way valve, a second automatic switching ten-way valve, a third quantitative ring, a fourth chromatographic column, a third carrier gas, an automatic switching four-way valve, a third exhaust valve, a fifth chromatographic column, a fourth exhaust valve, a fourth chromatographic column, a fifth chromatographic column and an argon-oxygen content measuring device, wherein the first automatic switching ten-way valve is connected with the second automatic switching ten-way valve, the third quantitative ring is connected with the third quantitative ring, the fourth chromatographic column is connected with the fourth quantitative ring, the third carrier gas is used for bringing the gas sample in the fourth quantitative ring into the fourth chromatographic column, the fourth chromatographic column is connected with the automatic switching four-way valve, the automatic switching four-way valve is communicated with the third exhaust valve used for exhausting hydrogen components passing through the fourth chromatographic column, the automatic switching four-way valve is communicated with the fifth chromatographic column for further separating argon and oxygen, and the third exhaust valve and the fifth chromatographic column are alternately communicated with the fourth chromatographic column, the fifth chromatographic column is communicated with the pulse discharge helium ionization detector through the second automatic switching six-way valve;
the ammonia and formaldehyde content measuring device comprises a sample storage passage communicated with the third automatic switching ten-way valve, the third automatic switching ten-way valve is communicated with a temperature-changing concentration desorber for concentrating a gas sample, the temperature-changing concentration desorber is communicated with the third automatic switching ten-way valve and is communicated with the sample storage passage at the sampling time phase, the third automatic switching ten-way valve is communicated with a sixth chromatographic column for separating ammonia and formaldehyde, the third automatic switching ten-way valve is communicated with a fourth carrier gas for introducing the gas sample in the sample storage passage into the sixth chromatographic column, and is communicated with a fourth exhaust valve for discharging components except the ammonia and the formaldehyde separated by the sixth chromatographic column, a seventh chromatographic column for further separating ammonia gas and formaldehyde is communicated between the third automatic switching ten-way valve and the second automatic switching six-way valve, and a fifth carrier gas for bringing the ammonia gas and the formaldehyde separated from the sixth chromatographic column and the seventh chromatographic column into the pulse discharge helium ionization detector is communicated with the third automatic switching ten-way valve;
the second automatic switching ten-way valve is communicated with a dew point transmitter for detecting moisture in a gas sample, and the first quantitative ring, the second quantitative ring, the third quantitative ring and the dew point transmitter are sequentially communicated along the flowing direction of the gas sample in the sampling process.
Compared with the prior art, the invention has the following technical effects:
firstly, in the process of measuring the content of the permanent gas, a gas sample is quantitatively sampled through a first quantitative ring, then in the actual use process, the gas sample to be measured is firstly quantified, then the gas to be measured in the quantified gas sample is detected, and the detection result of the whole gas sample is reflected by the quantitative sample detection result; the main component before hydrogen is discharged by the first exhaust valve, when the first chromatographic column of oxygen argon is separated, the first chromatographic column is communicated with the second chromatographic column, the oxygen argon is carried into the second chromatographic column, when the oxygen argon completely enters the second chromatographic column, the first chromatographic column is switched to be communicated with the first exhaust valve, and the main component after hydrogen is discharged. When nitrogen is separated from the first chromatographic column, the first chromatographic column is switched to be communicated with the second chromatographic column, nitrogen, methane and carbon monoxide are carried to the second chromatographic column, the content of the nitrogen, methane and carbon monoxide is detected by the pulse discharge helium ionization detector, and finally, the other part of separated permanent gas is discharged into the detection passage and is converged with the previously discharged permanent gas to complete the detection of the whole content of the permanent gas together, so that the separation of the permanent gas is completed in two times, the gas sample can be prevented from being separated once, excessive fuel hydrogen is generated, the flow time is too long in the process of passing through the first chromatographic column in large quantity, the separated permanent gas is easily separated from the first chromatographic column to cause inaccuracy of the detection result, the detection efficiency can be improved in two times, and the separation time is prevented from being lengthened due to excessive separation times, making the overall separation process time consuming too much.
Secondly, a second chromatographic column is arranged on the detection passage, the first carrier gas carries the separated permanent gas in the first chromatographic column to enter the second chromatographic column, the second chromatographic column performs secondary separation on the permanent gas, the separated permanent gas is equivalently separated again through the second chromatographic column, the separation degree of the permanent gas entering the pulse discharge helium ionization detector is ensured, the interference of the rest gas on the detection result is avoided, and the accuracy of the detection result is further ensured.
Thirdly, in the sampling process of the system, a gas sample sequentially flows through the first quantitative ring, the second quantitative ring and the third quantitative ring through the gas sample inlet and then enters the dew point transmitter, the gas sample sequentially fills the first quantitative ring, the second quantitative ring and the third quantitative ring, the gas sample enters the variable-temperature concentration desorber through the gas sample inlet, the gas sample is concentrated by the variable-temperature concentration desorber and then fills the sample storage passage, the gas sample can be collected by each quantitative ring and the variable-temperature concentration desorber through one-time sample introduction, the gas sample collected by each structure is further processed by each quantitative ring and the variable-temperature concentration desorber aiming at different detection purposes, the qualitative and quantitative determination are accurate, the components are not interfered with each other, and the detection efficiency of the system is improved.
Fourthly, the second automatic switching four-way valve is communicated with a pulse discharge helium ionization detector, and in the determination of the contents of the permanent gas component, the carbon dioxide component, the argon oxygen component and the ammonia formaldehyde component, each quantitative ring and the variable-temperature concentration desorber are communicated with the pulse discharge helium ionization detector by using each automatic switching valve, namely, the single pulse discharge helium ionization detector is used for completing the determination of various gas components, the structure of a system device is fully simplified, the number of detection devices is reduced, and further the use cost is effectively reduced.
Fifthly, still including the water content survey device who is used for detecting water, second automatic switch ten way valve intercommunication has the dew point transmitter that is arranged in detecting moisture in the gas sample, first ration ring, second ration ring, third ration ring and dew point transmitter communicate along gas sample flow direction in proper order at the sampling in-process, so in the in-process of carrying out system's sample, just namely after accomplishing the sample to first, second, three ration rings, can directly detect exhaust fuel hydrogen, and detect its moisture, can enough accomplish the sample work, can accomplish the detection work to moisture again, the structure of system's device has been simplified, detection efficiency is improved, use cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic diagram of a system sampling state;
FIG. 2 is a schematic view of a hydrogen purge state;
FIG. 3 is a schematic diagram showing the analysis and detection of oxygen, argon, nitrogen, methane and carbon monoxide states;
FIG. 4 is a schematic view of the analysis of the carbon dioxide status;
FIG. 5 is a schematic diagram illustrating the analysis and detection of the oxygen status of argon;
wherein, 1-a first automatic switching ten-way valve, 2-a second automatic switching ten-way valve, 3-a third automatic switching ten-way valve, 4-a first automatic switching six-way valve, 5-an automatic switching four-way valve, 6-a second automatic switching six-way valve, 6, 7-a gas sample inlet, 8-a first quantitative ring, 9-a second quantitative ring, 10-a temperature-changing concentration desorber, 11-a plane tee, 12-a dew point transducer, 13-a first chromatographic column, 14-a third chromatographic column, 15-a second chromatographic column, 16-a sixth chromatographic column, 17-a seventh chromatographic column, 18-a fifth chromatographic column, 19-a fourth chromatographic column, 20-a first carrier gas, 21-a second carrier gas, 22-a fifth carrier gas, 23-a fourth carrier gas and 24-a third carrier gas, 25-sixth carrier gas, 26-seventh carrier gas, 27-eighth carrier gas, 28-ninth carrier gas, 29-pulsed discharge helium ionization detector, 30-first vent valve, 31-fifth vent valve, 32-fourth vent valve, 33-second vent valve, 34-sixth vent valve, 35-seventh vent valve, 36-third vent valve, 37-planar four-way, 38-gas sample outlet, 39-third dosing ring, 40-tenth carrier gas.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a method and a system for measuring the content of a gas component in fuel hydrogen, which are used for solving the problems in the prior art, a first quantitative ring is used for quantifying the gas sample, a first chromatographic column is used for separating permanent gas, the quantified gas sample is evacuated through the first chromatographic column twice, the situation that the hydrogen component in the fuel hydrogen is evacuated once is avoided, the permanent gas is separated from the first chromatographic column due to excessive content of the hydrogen component, the subsequent measurement process of the permanent gas is inaccurate, a second chromatographic column is arranged for further separating the permanent gas, the separation degree of the permanent gas is improved, and the measurement accuracy is ensured.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Referring to fig. 1 to 5, the present invention provides a method for measuring the content of a gas component in fuel hydrogen, which includes a process for measuring the content of a permanent gas:
sampling: preparing a retention passage for retaining a gas sample, wherein the retention passage is provided with a first quantitative ring 8, introducing the gas sample into the retention passage, and quantitatively sampling the gas sample through the first quantitative ring 8;
separating and detecting a gas sample: switching the first chromatographic column 13 to be communicated with the first exhaust valve 30, discharging the main part of the hydrogen from the first exhaust valve, switching the first chromatographic column 13 to be communicated with the second chromatographic column 15 when the argon oxygen component is separated from the first chromatographic column 13, and completely putting the argon oxygen into the second chromatographic column 15 to be detected by the pulse discharge helium ionization detector 29. When argon and oxygen completely enter the second chromatographic column 15, the first chromatographic column 13 is switched to be communicated with the first exhaust valve 30, the main part of the hydrogen is discharged, when the nitrogen component is separated from the first chromatographic column 13, the first chromatographic column 13 is switched to be communicated with the second chromatographic column 15, and the nitrogen, methane and carbon monoxide component separated from the first chromatographic column 13 is detected by a pulse discharge helium ionization detector 29; in conclusion, the separation of the permanent gas is completed in two times, so that not only can the gas sample be prevented from being separated at one time, the fuel hydrogen is too much, the flow time is too long in the process of passing through the first chromatographic column 13 in a large amount, the separated permanent gas is easy to separate from the first chromatographic column 13, and the detection result is inaccurate, but also the detection efficiency can be improved as much as possible by completing the separation in two times, the separation time is prevented from being prolonged, and the loss time of the whole separation process is shortened.
Furthermore, a second chromatographic column 15 is arranged on the detection passage, the first carrier gas 20 carries the separated permanent gas in the first chromatographic column 13 to enter the second chromatographic column 15, the second chromatographic column 15 performs secondary separation on the permanent gas, and the rest gas is retained in the second chromatographic column 15, the separated permanent gas is further separated through the second chromatographic column 15, so that the separation degree of the permanent gas entering the pulse discharge helium ionization detector 29 is ensured, the rest gas is prevented from interfering the detection result, and the accuracy of the detection result is further ensured.
Further, the system sampling process before the permanent gas detection is included: a gas sample sequentially flows through a first quantitative ring 8, a second quantitative ring 9 and a third quantitative ring 39 through a gas sample inlet 7 and then enters a dew point transmitter 12, the gas sample sequentially fills the first quantitative ring 8, the second quantitative ring 9 and the third quantitative ring 39, the gas sample enters a temperature-changing concentration desorber 10 through the gas sample inlet 7, the gas sample is concentrated by the temperature-changing concentration desorber 10 and then fills a sample storage passage, the gas sample can be collected by each quantitative ring and the temperature-changing concentration desorber 10 through one-time sample introduction, the gas sample collected by each structure is further processed by each quantitative ring and the temperature-changing concentration desorber 10 according to different detection purposes, the qualitative and quantitative determination are accurate, the components are not interfered with each other, and the system detection efficiency is improved.
Further, the method comprises a water content determination process after the system sampling process: as the gas sample flows to dew point transmitter 12, moisture in the gas sample is directly read by dew point transmitter 12.
Further, a capnometry process is included after the system sampling process: the second carrier gas 21 carries the gas sample in the second quantitative ring 9 to enter the third chromatographic column 14, the third chromatographic column 14 intercepts carbon dioxide, the rest gas enters the second exhaust valve 33 to be discharged, the communication between the third chromatographic column 14 and the second exhaust valve 33 is cut off, the second carrier gas 21 carries the carbon dioxide in the third chromatographic column 14 to enter the pulse discharge helium ionization detector 29, the pulse discharge helium ionization detector 29 is used for determining the content of the carbon dioxide, and the carbon dioxide component peak position is inserted between methane and carbon monoxide to ensure the accuracy of the detection of the carbon dioxide.
Further, an argon and oxygen determination process is included after the system sampling process: the third carrier gas 24 carries the gas sample in the third quantitative ring 39 to enter the fourth chromatographic column 19, the fourth chromatographic column 19 intercepts argon and oxygen, the rest gas enters the third exhaust valve 36 to be discharged, the communication between the fourth chromatographic column 19 and the third exhaust valve 36 is cut off, the third carrier gas 24 carries the argon and the oxygen separated from the fourth chromatographic column 19 to enter the fifth chromatographic column 18, the argon and the oxygen are separated again through the fifth chromatographic column 18 and then enter the pulse discharge helium ionization detector 29, and the content of the argon and the content of the oxygen are measured through the pulse discharge helium ionization detector 29.
Further, the method comprises an ammonia gas and formaldehyde determination process after the system sampling process: the fourth carrier gas 23 carries the concentrated gas sample in the sample storage passage to enter the sixth chromatographic column 16, the sixth chromatographic column 16 intercepts ammonia and formaldehyde, the rest gas enters the fourth exhaust valve 32 to be discharged, before the ammonia and the formaldehyde flow out of the sixth chromatographic column 16, the sixth chromatographic column 16 is cut off to be communicated with the fourth exhaust valve 32, the fifth carrier gas 22 carries the ammonia and the formaldehyde intercepted by the sixth chromatographic column 16 to enter the seventh chromatographic column 17, the seventh chromatographic column 17 further separates the ammonia and the formaldehyde, the separated ammonia and the formaldehyde enter the pulse discharge helium ionization detector 29, and the pulse discharge helium ionization detector 29 measures the content of the ammonia and the formaldehyde.
The measuring system adopts the center cutting and back blowing separation technology, and the trace moisture detecting unit and the full-automatic temperature-variable concentration desorption device are matched to analyze and detect the moisture (H) in the fuel hydrogen2O), oxygen (O)2) Nitrogen (N)2) Argon (Ar), IICarbon Oxide (CO)2) Carbon monoxide (CO), methane (CH)4) Ammonia (NH)3) Formaldehyde (CH)2O) and the like, and comprises a device for measuring the content of the permanent gas, wherein the device for measuring the content of the permanent gas comprises a retention passage for retaining a gas sample, a first quantitative ring 8 for storing the gas sample and a first chromatographic column 13 for separating the permanent gas from the gas sample are arranged in the retention passage, the first quantitative ring 8 and the first chromatographic column 13 are sequentially arranged along the gas flow direction, the outlet of the first chromatographic column 13 is communicated with a multi-way switching valve, the multi-way switching valve is communicated with a detection passage and a first exhaust valve 30 for exhausting hydrogen components in the gas sample, the detection passage is provided with a pulse discharge helium ionization detector for detecting the content of the permanent gas components, the first exhaust valve 30 and the pulse discharge helium ionization detector are respectively and alternately communicated with the first chromatographic column 13 through the multi-way switching valve, and the detection passage is provided with a second chromatographic column 15 for separating the permanent gas again, a second chromatographic column 15 communicates between the pulsed discharge helium ionization detector and the multi-way switching valve.
Further, the multi-way switching valve is a first automatic switching six-way valve 4, the first automatic switching six-way valve 4 is communicated with a first exhaust valve 30, an outlet of the first chromatographic column 13 and an inlet of the second chromatographic column 15, the first automatic switching six-way valve 4 is connected with a first automatic switching ten-way valve 1, the first automatic switching ten-way valve 1 is communicated with a gas sample inlet 7 and an inlet of the first quantitative ring 8, the first automatic switching ten-way valve 1 is communicated with a first carrier gas 20 used for bringing a gas sample in the first quantitative ring 8 into the first chromatographic column 13, and the first automatic switching six-way valve 4 is used for conducting all the channels without adopting the arrangement of all the reversing valves, so that the conduction efficiency is improved, and the system structure is simplified; as a preferred embodiment of the present invention, the sixth port, the fifth port and the fourth port of the first automatic switching six-way valve 4 are respectively communicated with the first vent valve 30, the outlet of the first chromatographic column 13 and the inlet of the second chromatographic column 15, the first automatic switching ten-way valve 1 is connected to the first automatic switching six-way valve 4, the first port and the tenth port of the first automatic switching ten-way valve 1 are respectively communicated with the gas sample inlet 7 and the inlet of the first quantitative ring 8, and the ninth port of the first automatic switching ten-way valve 1 is communicated with the first carrier gas 20 for bringing the gas sample in the first quantitative ring 8 into the first chromatographic column 13.
In the detection of the permanent gas, the first automatic switching ten-way valve 1 switches a conduction path, the first carrier gas 20 carries a gas sample in the first quantitative ring 8 to enter the first chromatographic column 13, the front main component of the hydrogen is discharged by the first exhaust valve 30, before the oxygen and argon are separated from the first chromatographic column 13, the oxygen and argon in the first chromatographic column 13 are all brought into the second chromatographic column 15, when the oxygen and argon are completely separated from the first chromatographic column 13 to the second chromatographic column 15, the first automatic switching six-way valve 4 switches a conduction path, the rear main component of the hydrogen passing through the first chromatographic column 13 is discharged by the first exhaust valve 30, before the nitrogen is separated from the first chromatographic column 13, the first automatic switching ten-way valve 1 switches a conduction path, the nitrogen, methane and carbon monoxide in the first chromatographic column 13 are all brought into the second chromatographic column 15, and sequentially pass through the fourth interface and the fifth interface of the second automatic switching six-way valve 6 and enter the pulse discharge helium detector 29 The content of the permanent gas is measured by a pulsed discharge helium ionization detector 29.
Further, the device comprises a carbon dioxide content measuring device matched with the permanent gas content measuring device, wherein the carbon dioxide content measuring device comprises a second quantitative ring 9 communicated with a first automatic switching ten-way valve 1, the first automatic switching ten-way valve 1 is communicated with a third chromatographic column 14 for separating carbon dioxide, the first automatic switching ten-way valve 1 is communicated with a second carrier gas 21 for bringing a gas sample in the second quantitative ring 9 into the third chromatographic column 14, the third chromatographic column 14 is connected with a second automatic switching six-way valve 6, the second automatic switching six-way valve 6 is communicated with a second vent valve 33 and a pulse helium discharge ionization detector 29 which are respectively and alternately communicated with the third chromatographic column 14, and the pulse helium discharge detector 29 is communicated with the second automatic switching six-way valve 6; as a preferred embodiment of the present invention, the second quantitative ring 9 is communicated between the third port and the sixth port of the first automatic switching ten-way valve 1, the fifth port of the first automatic switching ten-way valve 1 is communicated with the third chromatographic column 14, the fourth port of the first automatic switching ten-way valve 1 is communicated with the second carrier gas 21, the third chromatographic column 14 is communicated with the sixth port of the second automatic switching six-way valve 6, and the first port and the fifth port of the second automatic switching six-way valve 6 are respectively provided with the second exhaust valve 33 and the carbon dioxide detector which are alternately communicated with the third chromatographic column 14. The carbon dioxide detector and the pulse discharge helium ionization detector are pulse discharge helium ionization detectors 29, and the pulse discharge helium ionization detectors 29 are communicated with a fifth interface of the second automatic switching six-way valve 6.
The carbon dioxide determination process comprises the following steps: after passing through the fourth interface and the third interface of the first automatic switching ten-way valve 1 in sequence, the second carrier gas 21 carries the gas sample in the second quantitative ring 9 to enter the third chromatographic column 14 through the sixth interface and the fifth interface of the first automatic switching ten-way valve 1 in sequence, the third chromatographic column 14 intercepts carbon dioxide, the rest of the gas enters the second exhaust valve to be exhausted through the sixth interface and the first interface of the second automatic switching six-way valve 6 in sequence, the second automatic switching six-way valve 6 switches the conduction path, the second carrier gas 21 carries the carbon dioxide in the third chromatographic column 14 to enter the pulse discharge ionization detector 29 after passing through the sixth interface and the fifth interface of the second automatic switching six-way valve 6, and the pulse discharge helium ionization detector 29 determines the content of the carbon dioxide.
The device comprises a first automatic switching ten-way valve 1, a second automatic switching ten-way valve 2, a third quantitative ring 39 connected to the second automatic switching ten-way valve 2, a fourth chromatographic column 19 for separating argon and oxygen from a gas sample, a third carrier gas 24 for bringing the gas sample in the third quantitative ring 39 into the fourth chromatographic column 19, an automatic switching four-way valve 5 connected to an outlet of the fourth chromatographic column 19, a third exhaust valve 36 for exhausting hydrogen components passing through the fourth chromatographic column 19, a fifth chromatographic column 18 for further separating the argon and the oxygen, wherein the third exhaust valve 36 and the fifth chromatographic column 18 are alternately communicated with the fourth chromatographic column 19, the fifth chromatographic column 18 is communicated with a pulse discharge helium ionization detector 29 through a second automatic switching six-way valve 6;
in a preferred embodiment of the present invention, the third quantitative loop 39 is connected between the third port and the tenth port of the second automatic switching ten-way valve 2, the fourth chromatographic column 19 is disposed between the sixth port and the ninth port of the second automatic switching ten-way valve 2, the fourth port of the second automatic switching ten-way valve 2 is communicated with the third carrier gas 24, the second port of the automatic switching four-way valve 5 is communicated with the third exhaust valve 36, the fourth port of the automatic switching four-way valve 5 is communicated with the fifth chromatographic column 18, the third exhaust valve 36 and the fifth chromatographic column 18 are alternately communicated with the fourth chromatographic column 19, and the fifth chromatographic column 18 is communicated with the pulsed discharge helium ionization detector 29 through the sixth port of the second automatic switching six-way valve 6.
In the process of measuring argon and oxygen, after passing through the fourth interface and the third interface of the second automatic switching ten-way valve 2 in sequence, the third carrier gas 24 carrying the gas sample in the third quantitative ring 39 enters the fourth chromatographic column 19 through the tenth interface and the ninth interface of the second automatic switching ten-way valve 2 in sequence, the fourth chromatographic column 19 intercepts argon and oxygen, hydrogen enters the third exhaust valve 36 through the sixth interface and the fifth interface of the second automatic switching ten-way valve 2 in sequence and the first interface and the second interface of the automatic switching four-way valve 5 in sequence and is discharged, the automatic switching four-way valve 5 switches the conduction path, the third carrier gas 24 carrying argon and oxygen separated from the fourth chromatographic column 19 enters the fifth chromatographic column 18 through the sixth interface and the fifth interface of the second automatic switching ten-way valve 2 in sequence and the first interface and the fourth interface of the automatic switching four-way valve 5 in sequence, and after separating argon and oxygen again through the fifth chromatographic column 18, the argon gas enters a pulse discharge helium ionization detector 29 through a sixth interface and a fifth interface of the second automatic switching six-way valve 6 in sequence, and the contents of the argon gas and the oxygen gas are measured by the pulse discharge helium ionization detector 29;
the ammonia and formaldehyde content measuring device is used for detecting ammonia and formaldehyde, the second automatic switching ten-way valve 2 is connected with a third automatic switching ten-way valve 3, the ammonia and formaldehyde content measuring device comprises a sample storage passage communicated with the third automatic switching ten-way valve 3, the third automatic switching ten-way valve 3 is communicated with a temperature-changing concentration desorber 10 used for concentrating a gas sample, so that the minimum detection concentration can reach nmol/mol, the temperature-changing concentration desorber 10 is communicated with the third automatic switching ten-way valve 3 and is communicated with the sample storage passage at the sampling time phase, the third automatic switching ten-way valve 3 is communicated with a sixth chromatographic column 16 used for separating ammonia and formaldehyde, the third automatic switching ten-way valve 3 is communicated with a fourth carrier gas 23 used for introducing the gas sample in the sample storage passage into the sixth chromatographic column 16, and the third automatic switching ten-way valve 3 is communicated with a fourth exhaust valve 32 used for exhausting components except ammonia and formaldehyde in the sixth chromatographic column 16, a seventh chromatographic column 17 for further separating ammonia gas and formaldehyde is communicated between the third automatic switching ten-way valve 3 and the second automatic switching six-way valve 6, and a fifth carrier gas 22 for bringing the ammonia gas and the formaldehyde separated from the sixth chromatographic column 16 and the seventh chromatographic column 17 into the pulse discharge helium ionization detector 29 is communicated with the third automatic switching ten-way valve 3;
in a preferred embodiment of the present invention, the sample storage path is communicated between the third port and the tenth port of the third automatic switching ten-way valve 3, the first port of the third automatic switching ten-way valve 3 is communicated with the temperature change concentrated desorber 10, the temperature change concentrated desorber 10 is communicated with the first port of the third automatic switching ten-way valve 3, and is communicated with the sample storage passage during sampling, a sixth chromatographic column 16 is communicated between the sixth interface and the ninth interface of the third automatic switching ten-way valve 3, a fourth carrier gas 23 is communicated with the fourth interface of the third automatic switching ten-way valve 3, a fifth interface of the third automatic switching ten-way valve 3 is communicated with a fourth exhaust valve 32, a seventh chromatographic column 17 is communicated between the seventh interface of the third automatic switching ten-way valve 3 and the sixth interface of the second automatic switching six-way valve 6, and a fifth carrier gas 22 is communicated with the eighth interface of the third automatic switching ten-way valve 3.
In the process of measuring ammonia gas and formaldehyde, after passing through the fourth interface and the third interface of the third automatic switching ten-way valve 3 in sequence, the fourth carrier gas 23 sequentially passes through the tenth interface and the ninth interface of the third automatic switching ten-way valve 3 in sequence, the gas sample concentrated in the carried sample storage passage sequentially passes through the tenth interface and the ninth interface of the third automatic switching ten-way valve 3 and then flows into the sixth chromatographic column 16, the sixth chromatographic column 16 intercepts ammonia gas and formaldehyde, the rest gas sequentially passes through the sixth interface and the fifth interface of the third automatic switching ten-way valve 3 and then enters the fourth exhaust valve 32 to be emptied, before the ammonia gas and the formaldehyde flow out of the sixth chromatographic column 16, the third automatic switching ten-way valve 3 switches the conduction path, the fifth carrier gas 22 carries the ammonia gas and the formaldehyde intercepted by the sixth chromatographic column 16 out through the eighth interface and the ninth interface of the third automatic switching ten-way valve 3 and then sequentially passes through the sixth interface and the seventh interface of the third automatic switching ten-way valve 3 and then enters the seventh chromatographic column 17, the seventh chromatographic column 17 further separates ammonia gas and formaldehyde, the separated ammonia gas and formaldehyde enter the pulse discharge helium ionization detector 29 through the sixth interface and the fifth interface of the second automatic switching six-way valve 6 in sequence, and the content of ammonia gas and formaldehyde is measured by the pulse discharge helium ionization detector 29
Preferably, the second automatic switching four-way valve 5 is communicated with a pulse discharge helium ionization detector 29, and in the determination of the contents of the permanent gas component, the carbon dioxide component, the argon oxygen component and the ammonia formaldehyde component, each quantitative ring, the temperature-changing concentration desorber 10 and the pulse discharge helium ionization detector 29 are communicated by using each automatic switching valve, that is, the determination of various gas components is completed by using a single pulse discharge helium ionization detector 29, the structure of a system device is fully simplified, the number of detection devices is reduced, and the use cost is effectively reduced.
Still including the water content survey device who is used for detecting water, second automatic switch ten way valve 2 intercommunication has dew point transmitter 12 that is arranged in detecting moisture in the gas sample, first ration ring 8, second ration ring 9, third ration ring 39 and dew point transmitter 12 communicate along gas sample flow direction in proper order at the sampling process, so at the in-process that carries out system's sample, just also accomplish first, two, the sample back of three ration rings, can directly detect tail gas, and detect its moisture, can enough accomplish sample work, can accomplish the detection achievement to moisture again, the structure of system's device has been simplified, and the detection efficiency is improved, and the use cost is reduced.
In order to ensure one-time sample feeding of the system device, a second interface of the second automatic switching ten-way valve 2 is communicated with a dew point transmitter 12, a gas sample inlet 7 and gasA first interface and a tenth interface of the first automatic switching ten-way valve 1, a first quantitative ring 8, a seventh interface and a sixth interface of the first automatic switching ten-way valve 1, a second quantitative ring 9, a third interface and a second interface of the first automatic switching ten-way valve 1, a first interface and a tenth interface of the second automatic switching ten-way valve 2, a third quantitative ring 39, a third interface and a second interface of the second automatic switching ten-way valve 2 are sequentially communicated between the sample outlets 38 along the gas flow direction, and preferably, a dew point transmitter 12 is communicated with the second interface of the second automatic switching ten-way valve 2; in the specific sampling process, a gas sample sequentially flows through a first interface and a tenth interface of the first automatic switching ten-way valve 1, a first quantitative ring 8, a seventh interface and a sixth interface of the first automatic switching ten-way valve 1, a second quantitative ring 9, a third interface and a second interface of the first automatic switching ten-way valve 1, a first interface and a tenth interface of the second automatic switching ten-way valve 2, a third quantitative ring 39, a third interface and a second interface of the second automatic switching ten-way valve 2 through a gas sample inlet 7, flows out of the second interface of the second automatic switching ten-way valve 2, enters the dew point transmitter 12, and fills the first quantitative ring 8, the second quantitative ring 9 and the third quantitative ring 39 with the gas sample; the gas sample flows out after sequentially flowing through the temperature-changing concentration desorber 10 and the first interface, the tenth interface, the third interface and the second interface of the third automatic switching ten-way valve 3 through the gas sample inlet 7, and the gas sample is concentrated by the temperature-changing concentration desorber 10 and then filled in the sample storage passage; and when the gas sample flows to the dew point transmitter 12, the moisture in the gas sample is directly read by the dew point transmitter 12, and the moisture (H) in the fuel hydrogen is completely separated and detected in each detection path2O), oxygen (O)2) Nitrogen (N)2) Argon (Ar), carbon dioxide (CO)2) Carbon monoxide (CO), methane (CH)4) Ammonia (NH)3) Formaldehyde (CH)2O), and the like. The qualitative and quantitative determination is accurate, the components do not interfere with each other, the separation degree R is more than or equal to 1.5, and the minimum detection concentration can reach nmol/mol. Preferably, a planar tee 11 is arranged at the gas sample inlet 7, and the other two interfaces of the planar tee 11 are respectively communicated with the temperature-changing concentration desorber 10 and the first interface of the first automatic switching ten-way valve 1. And preferably in the first automationA plane four-way valve 37 is arranged among the ten-way switching valve 1, the third automatic switching valve 3, the four-way automatic switching valve 5 and the six-way automatic switching valve 6 so as to communicate each channel at the pulse discharge helium ionization detector 29, and four interfaces of the plane four-way valve 37 are respectively communicated with a fifth interface of the ten-way automatic switching valve 1, a seventh interface of the ten-way automatic switching valve 3, a fourth interface of the four-way automatic switching valve 5 and a sixth interface of the six-way automatic switching valve 6.
Preferably, each exhaust valve adopts a needle valve structure, and the flow path of each needle valve is small, so that the amount of other gases discharged each time can be accurately controlled, and in order to avoid blockage of the needle valve structure in the use process, carrier gases are utilized to perform back-blowing dredging on the corresponding exhaust valve, specifically, sixth carrier gas 25 is communicated with an eighth interface of the second automatic switching ten-way valve 2, seventh carrier gas 26 is communicated with a third interface of the first automatic switching six-way valve 4, eighth carrier gas 27 is communicated with a second interface of the second automatic switching six-way valve 6, ninth carrier gas 28 is communicated with a third interface of the automatic switching four-way valve 5, and tenth carrier gas 40 is communicated with a first interface of the first automatic switching six-way valve 4; the fifth exhaust valve 31 is communicated with the second interface of the first automatic switching six-way valve 4, the sixth exhaust valve 34 is communicated with the third interface of the second automatic switching six-way valve 6, and the seventh exhaust valve 35 is communicated with the seventh interface of the second automatic switching ten-way valve 2; during purging, the first exhaust valve 30 is in communication with the tenth carrier gas 40, the second exhaust valve 33 is in communication with the eighth carrier gas 27, the third exhaust valve 36 is in communication with the ninth carrier gas 28, the fourth exhaust valve 32 is in communication with the fourth carrier gas 23, the fifth exhaust valve 31 is in communication with the seventh carrier gas 26, the sixth exhaust valve 34 is in communication with the eighth carrier gas 27, and the seventh exhaust valve 35 is in communication with the sixth carrier gas 25.
The adaptation according to the actual needs is within the scope of the invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
The principle and the implementation mode of the invention are explained by applying a specific example, and the description of the embodiment is only used for helping to understand the method and the core idea of the invention; meanwhile, for a part of those skilled in the art, according to the idea of the present invention, there may be variations in the embodiments and the application range. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. A method for measuring the content of a gas component in fuel hydrogen, characterized by comprising a process for measuring the content of a permanent gas:
sampling: preparing a retention passage, wherein the retention passage is provided with a first quantitative ring, introducing a gas sample into the retention passage, and quantitatively sampling the gas sample through the first quantitative ring;
and (3) detection: the main component before hydrogen is discharged by the first exhaust valve, when the first chromatographic column of oxygen argon is separated, the first chromatographic column is communicated with the second chromatographic column, the oxygen argon is carried into the second chromatographic column, when the oxygen argon completely enters the second chromatographic column, the first chromatographic column is switched to be communicated with the first exhaust valve, and the main component after hydrogen is discharged. When the nitrogen is separated from the first chromatographic column, the first chromatographic column is switched to be communicated with the second chromatographic column, the nitrogen, methane and carbon monoxide are carried to the second chromatographic column, and the content of the nitrogen, methane and carbon monoxide is measured by a pulse discharge helium ionization detector.
2. The method for determining the content of the gas component in the fuel hydrogen as claimed in claim 1, wherein a second chromatographic column is disposed on the detection passage, the first carrier gas carries the permanent gas in the first chromatographic column into the second chromatographic column, and the second chromatographic column separates the permanent gas.
3. A method for determining the content of a gas component in fuel hydrogen as claimed in claim 1 or 2, characterized by comprising, during sampling of the system before detection of the permanent gas:
a gas sample sequentially flows through a first quantitative ring, a second quantitative ring and a third quantitative ring through a gas sample inlet and then enters a dew point transmitter, and the first quantitative ring, the second quantitative ring and the third quantitative ring quantitatively measure the gas sample sequentially;
and the gas sample enters the temperature-changing concentration desorber through the gas sample inlet, and the gas sample is concentrated by the temperature-changing concentration desorber and then filled in the sample storage passage.
4. A method of measuring a gas component content in fuel hydrogen as claimed in claim 3, characterized by comprising a water content measuring process after the system sampling process of:
as the gas sample flows to the dew point transmitter, the moisture in the gas sample is read directly by the dew point transmitter.
5. The method for determining the content of a gaseous component in fuel hydrogen of claim 4, characterized by comprising a carbon dioxide determination process after the system sampling process:
and the second carrier gas carries the gas sample in the second quantitative ring to enter a third chromatographic column, the third chromatographic column intercepts carbon dioxide, the rest gas enters a second exhaust valve to be exhausted, the communication between the third chromatographic column and the second exhaust valve is cut off, the second carrier gas carries the carbon dioxide in the third chromatographic column to enter a pulse discharge helium ionization detector, and the content of the carbon dioxide is measured by the pulse discharge helium ionization detector.
6. The method for determining the content of a gaseous component in fuel hydrogen of claim 5, comprising an argon, oxygen determination process following the system sampling process:
and the third carrier gas carries the sample in the third quantitative ring to enter a fourth chromatographic column, hydrogen pre-separated by the fourth chromatographic column is discharged through a third exhaust valve, when the hydrogen is completely discharged through the third exhaust valve, the connection with the third exhaust valve is cut off, argon oxygen components separated by the fourth chromatographic column are carried to a fifth chromatographic column, when argon oxygen in the fourth chromatographic column completely enters the fifth chromatographic column, the fourth chromatographic column is switched to be communicated with a seventh exhaust valve, the sixth carrier gas carries gas components outside the fourth chromatographic column to be discharged through a seventh exhaust valve, meanwhile, the fifth chromatographic column is switched to be communicated with a pulse discharge helium ionization detector, and the argon oxygen components further separated by the third carrier gas carrying the fifth chromatographic column are detected by the pulse discharge helium ionization detector.
7. The method for determining the content of a gaseous component in fuel hydrogen of claim 6, comprising an ammonia and formaldehyde determination process following the system sampling process:
and the fourth carrier gas carries the concentrated gas sample in the sample storage passage to enter a sixth chromatographic column, the sixth chromatographic column intercepts ammonia and formaldehyde, the rest gas enters a fourth exhaust valve to be exhausted, before the ammonia and the formaldehyde flow out of the sixth chromatographic column, the communication between the sixth chromatographic column and the fourth exhaust valve is cut off, the fifth carrier gas carries the ammonia and the formaldehyde intercepted by the sixth chromatographic column to enter a seventh chromatographic column, the seventh chromatographic column further separates the ammonia and the formaldehyde, the separated ammonia and the formaldehyde enter a pulse discharge helium ionization detector, and the content of the ammonia and the formaldehyde is measured by the pulse discharge helium ionization detector.
8. A system for measuring the content of gas components in fuel hydrogen is characterized by comprising a permanent gas content measuring device, the permanent gas content measuring device comprises a retention passage, a first quantitative ring and a first chromatographic column are arranged in the retention passage, the first quantitative ring and the first chromatographic column are sequentially arranged along the gas flowing direction, the outlet of the first chromatographic column is communicated with a multi-way switching valve, the multi-way switching valve is communicated with a detection passage and a first exhaust valve, the detection passage is provided with a pulse discharge helium ionization detector, the first exhaust valve and the pulse discharge helium ionization detector are respectively communicated with the first chromatographic column through the multi-way switching valve in an alternating way, and a second chromatographic column is arranged on the detection channel and communicated between the pulse discharge helium ionization detector and the multi-way switching valve.
9. The system for determining the gas component content in fuel hydrogen according to claim 8, wherein the multi-way switching valve is a first automatic switching six-way valve, the first automatic switching six-way valve communicates with the first exhaust valve, the outlet of the first chromatography column and the inlet of the second chromatography column, the first automatic switching six-way valve is connected with a first automatic switching ten-way valve, the first automatic switching ten-way valve communicates with a gas sample inlet and the inlet of a first quantitative ring, and the first automatic switching ten-way valve communicates with a first carrier gas for bringing a gas sample in the first quantitative ring into the first chromatography column.
10. The system for determining the content of a gas component in fuel hydrogen according to claim 9, further comprising a carbon dioxide content determining means provided in association with the permanent gas content determining means, the carbon dioxide content measuring device comprises a second quantitative ring communicated with the first automatic switching ten-way valve, the first automatic switching ten-way valve is communicated with a third chromatographic column for separating carbon dioxide, the first automatic switching ten-way valve is communicated with a second carrier gas for bringing the gas sample in the second quantitative ring into the third chromatographic column, the third chromatographic column is connected with a second automatic switching six-way valve, the second automatic switching six-way valve is communicated with a second exhaust valve and a pulse discharge helium ionization detector which are respectively and alternately communicated with the third chromatographic column, and the pulse discharge helium ionization detector is communicated with the second automatic switching six-way valve;
the argon-oxygen content measuring device comprises a first automatic switching ten-way valve, a second automatic switching ten-way valve, a third quantitative ring, a fourth chromatographic column, a third carrier gas, an automatic switching four-way valve, a third exhaust valve, a fifth chromatographic column, a fourth exhaust valve, a fourth chromatographic column, a fifth chromatographic column and an argon-oxygen content measuring device, wherein the first automatic switching ten-way valve is connected with the second automatic switching ten-way valve, the third quantitative ring is connected with the third quantitative ring, the fourth chromatographic column is connected with the fourth quantitative ring, the third carrier gas is used for bringing the gas sample in the fourth quantitative ring into the fourth chromatographic column, the fourth chromatographic column is connected with the automatic switching four-way valve, the automatic switching four-way valve is communicated with the third exhaust valve used for exhausting hydrogen components passing through the fourth chromatographic column, the automatic switching four-way valve is communicated with the fifth chromatographic column for further separating argon and oxygen, and the third exhaust valve and the fifth chromatographic column are alternately communicated with the fourth chromatographic column, the fifth chromatographic column is communicated with the pulse discharge helium ionization detector through the second automatic switching six-way valve;
the ammonia and formaldehyde content measuring device comprises a sample storage passage communicated with the third automatic switching ten-way valve, the third automatic switching ten-way valve is communicated with a temperature-changing concentration desorber for concentrating a gas sample, the temperature-changing concentration desorber is communicated with the third automatic switching ten-way valve and is communicated with the sample storage passage at the sampling time phase, the third automatic switching ten-way valve is communicated with a sixth chromatographic column for separating ammonia and formaldehyde, the third automatic switching ten-way valve is communicated with a fourth carrier gas for introducing the gas sample in the sample storage passage into the sixth chromatographic column, and is communicated with a fourth exhaust valve for discharging components except the ammonia and the formaldehyde separated by the sixth chromatographic column, a seventh chromatographic column for further separating ammonia gas and formaldehyde is communicated between the third automatic switching ten-way valve and the second automatic switching six-way valve, and a fifth carrier gas for bringing the ammonia gas and the formaldehyde separated from the sixth chromatographic column and the seventh chromatographic column into the pulse discharge helium ionization detector is communicated with the third automatic switching ten-way valve;
the second automatic switching ten-way valve is communicated with a dew point transmitter for detecting moisture in a gas sample, and the first quantitative ring, the second quantitative ring, the third quantitative ring and the dew point transmitter are sequentially communicated along the flowing direction of the gas sample in the sampling process.
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