CN116466002A - Single TCD-based hydrogen and non-hydrogen component measurement device and method - Google Patents
Single TCD-based hydrogen and non-hydrogen component measurement device and method Download PDFInfo
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- CN116466002A CN116466002A CN202310475504.8A CN202310475504A CN116466002A CN 116466002 A CN116466002 A CN 116466002A CN 202310475504 A CN202310475504 A CN 202310475504A CN 116466002 A CN116466002 A CN 116466002A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 96
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 96
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000005259 measurement Methods 0.000 title claims description 26
- 239000007789 gas Substances 0.000 claims abstract description 45
- 239000012159 carrier gas Substances 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000001307 helium Substances 0.000 claims description 15
- 229910052734 helium Inorganic materials 0.000 claims description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 7
- 238000000691 measurement method Methods 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 description 13
- 238000001514 detection method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000357 thermal conductivity detection Methods 0.000 description 1
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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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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention provides a single TCD-based hydrogen and non-hydrogen component measuring device and a single TCD-based hydrogen and non-hydrogen component measuring method, wherein the single TCD-based hydrogen and non-hydrogen component measuring device comprises a first multi-way valve, a first chromatographic column and a first quantitative ring, two ends of the first quantitative ring and the first chromatographic column are respectively communicated with a port of the first multi-way valve, and a first reference gas and a first carrier gas are respectively communicated with a port of the first multi-way valve; further comprises: one end of the second chromatographic column is communicated with the port of the first multi-way valve, and the other end of the second chromatographic column is connected with the second channel of only one TCD; the third chromatographic column and two ends of the second quantitative ring are communicated with the port of the second multi-way valve; the second reference gas and the second carrier gas are respectively communicated with the ports of the second multi-way valve; the port of the second multi-way valve is communicated with the port of the third multi-way valve; the two ends of the fourth chromatographic column are respectively communicated with the ports of a third multi-way valve, and the ports of the third multi-way valve are communicated with the first channel of the TCD. The invention has the advantages of low cost and the like.
Description
Technical Field
The present invention relates to chromatographic technology, and is especially one single TCD-based hydrogen and non-hydrogen component measuring apparatus and method.
Background
The detector for measurement matching of hydrogen and permanent non-hydrogen components in ppm to percentage order is a Thermal Conductivity Detector (TCD), which is a detector that outputs a voltage signal based on the difference in thermal conductivity between the carrier gas and the sample to be measured to achieve detection of the substance, TCD generally has two channels, measurement and reference, output signal = measurement-reference, in order to reduce the effect of temperature, flow variations on TCD noise. The greater the difference in thermal conductivity between the carrier gas and the sample gas, the more excellent the response is obtained for the analyte. The carrier gases commonly used in TCD detectors include hydrogen, helium, and nitrogen, wherein helium and hydrogen are commonly used to perform analytical measurement of non-hydrogen components, nitrogen is used to perform analytical measurement of hydrogen components, and some manufacturers also use helium as a carrier gas to perform measurement of hydrogen.
At present, the analysis method for realizing hydrogen and non-hydrogen components comprises the following steps: the hydrogen and the non-hydrogen components are separated through a chromatographic column system and a valve, and then are respectively introduced into different TCD detectors to realize detection, 2 TCD detectors are needed to be matched in the system, and analysis and measurement on the same 1 TCD are not realized.
1. Separating hydrogen: the hydrogen-containing component and the non-hydrogen component are separated by a chromatographic column system + valve cut, and the hydrogen component detection is achieved by a TCD detector 1 using nitrogen as carrier gas.
2. Separation of non-hydrogen components: the separation of the non-hydrogen components is realized through a chromatographic column system and a valve, and the detection of the non-hydrogen components is realized through a TCD detector 2 taking hydrogen as carrier gas.
From the above, the prior art method has the following problems:
1. after the hydrogen and the non-hydrogen components are separated through a column system and a valve, the hydrogen and the non-hydrogen components respectively enter 1 TCD detector for measurement, and the number of detectors of the chromatographic system is 2, thereby increasing the complexity and the cost of the system.
2. The 2 TCDs in the system require an additional 2-way supply for the purpose of carrier gas consumption only for reference and not for detection, increasing carrier gas costs and maintenance costs for carrier gas replacement.
Disclosure of Invention
To solve the above-mentioned shortcomings in the prior art, the present invention provides a hydrogen and non-hydrogen component measuring device based on a single TCD.
The invention aims at realizing the following technical scheme:
the single TCD-based hydrogen and non-hydrogen component measuring device comprises a first multi-way valve, a first chromatographic column and a first quantitative ring, wherein two ends of the first quantitative ring and the first chromatographic column are respectively communicated with ports of the first multi-way valve, and a first reference gas and a first carrier gas are respectively communicated with ports of the first multi-way valve; the single TCD-based hydrogen and non-hydrogen component measurement device further includes:
one end of the second chromatographic column is communicated with the port of the first multi-way valve, and the other end of the second chromatographic column is connected with a second channel of only one TCD;
the two ends of the third chromatographic column and the second quantitative ring are communicated with the port of the second multi-way valve; the second reference gas and the second carrier gas are respectively communicated with the ports of the second multi-way valve; the port of the second multi-way valve is communicated with the port of the third multi-way valve;
the device comprises a third multi-way valve and a fourth chromatographic column, wherein two ends of the fourth chromatographic column are respectively communicated with a port of the third multi-way valve, and the port of the third multi-way valve is communicated with a first channel of the TCD.
The invention also aims to provide a single TCD-based hydrogen and non-hydrogen component measurement method, which is realized by the following technical scheme:
the method for measuring the hydrogen and the non-hydrogen components based on the single TCD comprises the following steps:
switching to a first state, wherein the sample gas sequentially passes through the first quantitative ring and the second quantitative ring, and simultaneously, the first reference gas sequentially passes through the first multi-way valve, the second chromatographic column and the second channel of only one TCD, and the second reference gas sequentially passes through the second multi-way valve, the third multi-way valve and the first channel of only one TCD; two ends of the first quantitative ring are respectively communicated with the port of the first multi-way valve, and two ends of the second quantitative ring are communicated with the port of the second multi-way valve;
when switching to the second state, the first carrier gas sequentially passes through the first quantitative ring, the first chromatographic column, the second chromatographic column and the second channel, and the second carrier gas sequentially passes through the second quantitative ring, the third chromatographic column, the fourth chromatographic column and the first channel; the two ends of the first chromatographic column are respectively communicated with the port of the first multi-way valve, the two ends of the third chromatographic column and the second quantitative ring are respectively communicated with the port of the second multi-way valve, and the two ends of the fourth chromatographic column are respectively communicated with the port of the third multi-way valve.
Compared with the prior art, the invention has the following beneficial effects:
1. the structure is simple, and the cost is low;
the retention time difference of the components to be analyzed is utilized to realize that 2 channels of TCD are mutually reference and measurement channels, so that the measurement of hydrogen and non-hydrogen components is realized by single TCD;
2. the working performance is good;
when single TCD is applied to non-identical carrier gases (reference, measurement), the measurement-reference can be realized to reduce the noise of TCD without changing the TCD response;
the first reference gas and the first carrier gas adopt nitrogen or helium, and the second reference gas and the second carrier gas adopt hydrogen or helium, so that the consumption of adding additional gas for a reference flow path of the TCD detector is avoided.
Drawings
The present disclosure will become more readily understood with reference to the accompanying drawings. As will be readily appreciated by those skilled in the art: the drawings are only for illustrating the technical scheme of the present invention and are not intended to limit the scope of the present invention. In the figure:
FIG. 1 is a schematic diagram of the structure of a hydrogen and non-hydrogen constituent measurement apparatus based on a single TCD according to an embodiment of the invention.
Detailed Description
Fig. 1 and the following description depict alternative embodiments of the invention to teach those skilled in the art how to make and reproduce the invention. For the purpose of explaining the technical solution of the present invention, some conventional aspects have been simplified or omitted. Those skilled in the art will appreciate variations or alternatives derived from these embodiments that fall within the scope of the invention. Those skilled in the art will appreciate that the features described below can be combined in various ways to form multiple variations of the invention. Thus, the invention is not limited to the following alternative embodiments, but only by the claims and their equivalents.
Example 1:
fig. 1 schematically shows a structural diagram of a single TCD-based hydrogen and non-hydrogen composition measuring apparatus according to an embodiment of the present invention, as shown in fig. 1, including:
the device comprises a first multi-way valve 11, a first chromatographic column 31 and a first quantitative ring 21, wherein two ends of the first quantitative ring 21 and the first chromatographic column 31 are respectively communicated with a port of the first multi-way valve 11, and a first reference gas 51 and a first carrier gas 52 are respectively communicated with a port of the first multi-way valve 11;
a second chromatographic column 32 and a TCD40, one end of the second chromatographic column 32 is connected to the port of the first multi-way valve 11, and the other end is connected to a second channel 42 of only one TCD 40;
a second multi-way valve 12, a third chromatographic column 33 and a second quantitative ring 22, wherein two ends of the third chromatographic column 33 and the second quantitative ring 22 are communicated with a port of the second multi-way valve 12; a second reference gas 61 and a second carrier gas 62 are respectively communicated with ports of the second multi-way valve 12; the port of the second multi-way valve 12 is communicated with the port of the third multi-way valve 13;
a third multi-way valve 13 and a fourth chromatographic column 34, wherein two ends of the fourth chromatographic column 34 are respectively communicated with a port of the third multi-way valve 13, and a port of the third multi-way valve 13 is communicated with a first channel 41 of the TCD 40.
For accurate switching to achieve flow path communication, further, when switching to the first state, the sample gas sequentially passes through the first metering ring 21 and the second metering ring 22, and simultaneously, the first reference gas 51 sequentially passes through the first multi-way valve 11, the second chromatographic column 32 and the second channel 42, and the second reference gas 61 sequentially passes through the second multi-way valve 12, the third multi-way valve 13 and the first channel 41; when switching to the second state, the first carrier gas 52 passes through the first dosing ring 21, the first chromatography column 31, the second chromatography column 32, and the second channel 42 in this order, and the second carrier gas 62 passes through the second dosing ring 22, the third chromatography column 33, the fourth chromatography column 34, and the first channel 41 in this order.
In order to share the gas to reduce the cost, further, the first reference gas 51 and the first carrier gas 52 use nitrogen or helium, and the second reference gas 61 and the second carrier gas 62 use hydrogen or helium.
In order to obtain more non-hydrogen component content, further, the single TCD-based hydrogen and non-hydrogen component measurement device further includes:
a fifth chromatographic column 35, wherein one end of the fifth chromatographic column 35 is communicated with the port of the third multi-way valve 13, and the other end is communicated with the first channel 41.
In order to improve the operational reliability, further, the first multi-way valve 11, the second multi-way valve 12 and the third multi-way valve 13 are ten-way valves, respectively.
The method for measuring the hydrogen and the non-hydrogen components based on the single TCD comprises the following steps:
switching to the first state, the sample gas sequentially passes through the first dosing ring 21 and the second dosing ring 22, while the first reference gas 51 sequentially passes through the first multi-way valve 11, the second chromatographic column 32 and the second channel 42 (hydrogen measurement channel) of only one TCD40, and the second reference gas 61 sequentially passes through the second multi-way valve 12, the third multi-way valve 13 and the first channel 41 (non-hydrogen component measurement channel) of only one TCD 40; two ends of the first quantitative ring 21 are respectively communicated with the port of the first multi-way valve 11, and two ends of the second quantitative ring 22 are communicated with the port of the second multi-way valve 12;
when switching to the second state, the first carrier gas 52 passes through the first dosing ring 21, the first chromatography column 31, the second chromatography column 32, and the second channel 42 in this order, and the second carrier gas 62 passes through the second dosing ring 22, the third chromatography column 33, the fourth chromatography column 34, and the first channel 41 in this order; the two ends of the first chromatographic column 31 are respectively communicated with the ports of the first multi-way valve 11, the two ends of the third chromatographic column 33 and the second quantitative ring 22 are respectively communicated with the ports of the second multi-way valve 12, and the two ends of the fourth chromatographic column 34 are respectively communicated with the ports of the third multi-way valve 13.
In order to share the gas to reduce the cost, further, the first reference gas 51 and the first carrier gas 52 use nitrogen or helium, and the second reference gas 61 and the second carrier gas 62 use hydrogen or helium.
In order to obtain more non-hydrogen component content, a fifth chromatographic column is further arranged, one end of the fifth chromatographic column is communicated with a port of the third multi-way valve, and the other end of the fifth chromatographic column is communicated with the first channel.
Example 2:
application example of the single TCD-based hydrogen and non-hydrogen component measurement apparatus and method according to example 1 of the present invention.
In the present application example, as shown in fig. 1, the first multi-way valve 11, the second multi-way valve 12, and the third multi-way valve 13 are ten-way valves, respectively; both ends of the first chromatographic column 31 and the first quantitative ring 21 are respectively communicated with the ports of the first multi-way valve 11, and the first reference gas 51 and the first carrier gas 52 are respectively communicated with the ports of the first multi-way valve 11 by using nitrogen; only one TCD40, the first channel 41 being a non-hydrogen component measurement channel, communicates through the fifth column 35 with the port of the third multi-way valve 13, the second channel 42 being a hydrogen measurement channel, communicates through the second column 32 with the port of the first multi-way valve 11;
both ends of the second quantitative ring 22 and the third chromatographic column 33 are respectively communicated with the port of the second multi-way valve 12, and the second reference gas 61 and the second carrier gas 62 are respectively communicated with the port of the second multi-way valve 12 by adopting hydrogen;
both ends of the fourth chromatographic column 34 are communicated with the ports of the third multi-way valve 13, and the ports of the third multi-way valve 13 are communicated with the ports of the second multi-way valve 12.
The method for measuring the hydrogen and the non-hydrogen components based on the single TCD, namely the working process of the measuring device of the embodiment, comprises the following steps:
the three multi-way valves are switched to the first state, the sample gas sequentially passes through the first metering ring 21 and the second metering ring 22 in the forward direction, and at the same time, the first reference gas 51 sequentially passes through the first multi-way valve 11, the second chromatographic column 32 and the second channel 42 (hydrogen gas measurement channel) of only one TCD40, and the second reference gas 61 sequentially passes through the second multi-way valve 12, the third multi-way valve 13, the fifth chromatographic column 35 and the first channel 41 (non-hydrogen component measurement channel) of only one TCD 40;
when the three multi-way valves are switched to the second state, the first carrier gas 52 passes through the first dosing ring 21 (reverse pass), the first chromatography column 31, the second chromatography column 32, and the second channel 42 in this order, and the second carrier gas 62 passes through the second dosing ring 22 (reverse pass), the third chromatography column 33, the fourth chromatography column 34, the fifth chromatography column, and the first channel 41 in this order.
Example 3:
the application example of the single TCD-based hydrogen and non-hydrogen component measuring apparatus and method according to example 1 of the present invention is different from example 2 in that:
the first reference gas 51 and the first carrier gas 52 use helium, and the second reference gas 61 and the second carrier gas 62 use helium, that is, the same gas.
Claims (9)
1. The single TCD-based hydrogen and non-hydrogen component measuring device comprises a first multi-way valve, a first chromatographic column and a first quantitative ring, wherein two ends of the first quantitative ring and the first chromatographic column are respectively communicated with ports of the first multi-way valve, and a first reference gas and a first carrier gas are respectively communicated with ports of the first multi-way valve; the hydrogen and non-hydrogen component measuring device based on single TCD is characterized by further comprising:
one end of the second chromatographic column is communicated with the port of the first multi-way valve, and the other end of the second chromatographic column is connected with a second channel of only one TCD;
the two ends of the third chromatographic column and the second quantitative ring are communicated with the port of the second multi-way valve; the second reference gas and the second carrier gas are respectively communicated with the ports of the second multi-way valve; the port of the second multi-way valve is communicated with the port of the third multi-way valve;
the device comprises a third multi-way valve and a fourth chromatographic column, wherein two ends of the fourth chromatographic column are respectively communicated with a port of the third multi-way valve, and the port of the third multi-way valve is communicated with a first channel of the TCD.
2. The single TCD based hydrogen and non-hydrogen constituent measurement device according to claim 1, wherein when switching to the first state, the sample gas passes sequentially through the first dosing ring and the second dosing ring while the first reference gas passes sequentially through the first multi-way valve, the second chromatographic column and the second channel, and the second reference gas passes sequentially through the second multi-way valve, the third multi-way valve and the first channel; when switching to the second state, the first carrier gas sequentially passes through the first quantitative ring, the first chromatographic column, the second chromatographic column and the second channel, and the second carrier gas sequentially passes through the second quantitative ring, the third chromatographic column, the fourth chromatographic column and the first channel.
3. The single TCD based hydrogen and non-hydrogen constituent measurement device according to claim 2, wherein the first reference gas and first carrier gas are nitrogen or helium and the second reference gas and second carrier gas are hydrogen or helium.
4. The single TCD based hydrogen and non-hydrogen composition measurement device according to claim 1, further comprising:
and one end of the fifth chromatographic column is communicated with the port of the third multi-way valve, and the other end of the fifth chromatographic column is communicated with the first channel.
5. The single TCD based hydrogen and non-hydrogen composition measurement device according to claim 1, wherein the first, second and third multi-way valves are each ten-way valves.
6. The method for measuring the hydrogen and the non-hydrogen components based on the single TCD comprises the following steps:
switching to a first state, wherein the sample gas sequentially passes through the first quantitative ring and the second quantitative ring, and simultaneously, the first reference gas sequentially passes through the first multi-way valve, the second chromatographic column and the second channel of only one TCD, and the second reference gas sequentially passes through the second multi-way valve, the third multi-way valve and the first channel of only one TCD; two ends of the first quantitative ring are respectively communicated with the port of the first multi-way valve, and two ends of the second quantitative ring are communicated with the port of the second multi-way valve;
when switching to the second state, the first carrier gas sequentially passes through the first quantitative ring, the first chromatographic column, the second chromatographic column and the second channel, and the second carrier gas sequentially passes through the second quantitative ring, the third chromatographic column, the fourth chromatographic column and the first channel; the two ends of the first chromatographic column are respectively communicated with the port of the first multi-way valve, the two ends of the third chromatographic column and the second quantitative ring are respectively communicated with the port of the second multi-way valve, and the two ends of the fourth chromatographic column are respectively communicated with the port of the third multi-way valve.
7. The single TCD based hydrogen and non-hydrogen constituent measurement method according to claim 6, wherein the first reference gas and first carrier gas are nitrogen or helium and the second reference gas and second carrier gas are hydrogen or helium.
8. The single TCD based hydrogen and non-hydrogen constituent measurement method according to claim 6, further providing a fifth chromatographic column having one end communicating with the port of the third multi-way valve and the other end communicating with the first channel.
9. The single TCD based hydrogen and non-hydrogen constituent measurement method according to claim 6, wherein the first channel is a non-hydrogen constituent measurement channel and the second channel is a hydrogen measurement channel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211739745 | 2022-12-30 | ||
| CN2022117397450 | 2022-12-30 |
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| Publication Number | Publication Date |
|---|---|
| CN116466002A true CN116466002A (en) | 2023-07-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310475504.8A Pending CN116466002A (en) | 2022-12-30 | 2023-04-28 | Single TCD-based hydrogen and non-hydrogen component measurement device and method |
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| CN (1) | CN116466002A (en) |
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2023
- 2023-04-28 CN CN202310475504.8A patent/CN116466002A/en active Pending
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