Single-tcd based hydrogen and non-hydrogen component measurement device and method

Abstract

The application provides a hydrogen and non-hydrogen component measuring device and method based on single TCD, which 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 communicated with ports of the first multi-way valve, a first reference gas and a first carrier gas are communicated with ports of the first multi-way valve; further comprising: one end of a second chromatographic column is communicated with a port of the first multi-way valve, and the other end is connected with a second channel of only one TCD; two ends of a third chromatographic column and a second quantitative ring are communicated with ports of a second multi-way valve; a second reference gas and a second carrier gas are communicated with ports of the second multi-way valve; a port of the second multi-way valve is communicated with a port of a third multi-way valve; two ends of a fourth chromatographic column are respectively communicated with ports of the third multi-way valve, and a port of the third multi-way valve is communicated with a first channel of the TCD. The application has the advantages of low cost.

Description

Technical Field

[0001] This invention relates to chromatography techniques, and more particularly to a device and method for measuring hydrogen and non-hydrogen components based on a single TCD. Background Technology

[0002] For the measurement of hydrogen and permanent non-hydrogen components in the ppm to 100% range, the appropriate detector is a thermal conductivity detector (TCD). A TCD is a detector that detects substances by outputting a voltage signal based on the difference in thermal conductivity between the carrier gas and the sample. A TCD typically has two channels: a measurement channel and a reference channel. The output signal equals the measurement signal minus the reference signal, in order to reduce the impact of temperature and flow rate changes on TCD noise. The greater the difference in thermal conductivity between the carrier gas and the sample gas, the better the response to the analyte. Commonly used carrier gases for TCD detectors include hydrogen, helium, and nitrogen. Helium and hydrogen are commonly used for the analysis and measurement of non-hydrogen components, while nitrogen is used for the analysis and measurement of hydrogen components. Some manufacturers also use helium as a carrier gas for hydrogen measurement.

[0003] Currently, the method for analyzing hydrogen and non-hydrogen components involves separating hydrogen and non-hydrogen components using a chromatographic column system with valve cutting, and then passing them separately into different TCD detectors for detection. This system requires matching two TCD detectors, and it does not achieve analysis and measurement on the same TCD.

[0004] 1. Separation of hydrogen: Hydrogen-containing and non-hydrogen components are separated by a chromatographic column system and valve cutting, and hydrogen components are detected by a TCD detector 1 using nitrogen as the carrier gas.

[0005] 2. Separation of non-hydrogen components: Non-hydrogen components are separated by a chromatographic column system and valve cutting, and non-hydrogen components are detected by a TCD detector 2 using hydrogen as the carrier gas.

[0006] As can be seen from the above, the problems with existing technical methods are:

[0007] 1. After hydrogen and non-hydrogen components are separated by a column system and valve, each component is measured by a separate TCD detector. This requires two detectors for the chromatographic system, increasing the system's complexity and cost.

[0008] 2. The two TCDs in the system require two additional channels that are only used as references and do not serve the purpose of detection. This increases the carrier gas consumption, the cost of carrier gas, and the maintenance cost of replacing carrier gas. Summary of the Invention

[0009] To address the shortcomings of the existing technical solutions, the present invention provides a hydrogen and non-hydrogen component measurement device based on a single TCD.

[0010] The objective of this invention is achieved through the following technical solution:

[0011] A single-TCD-based hydrogen and non-hydrogen component measurement device, comprising a first multi-port valve, a first chromatographic column, and a first metering loop, wherein the two ends of the first metering loop and the first chromatographic column are respectively connected to the ports of the first multi-port valve, and a first reference gas and a first carrier gas are respectively connected to the ports of the first multi-port valve; the single-TCD-based hydrogen and non-hydrogen component measurement device further comprises:

[0012] The second chromatographic column and the TCD, one end of the second chromatographic column is connected to the port of the first multi-port valve, and the other end is connected to the second channel of the only TCD;

[0013] A second multi-way valve, a third chromatographic column, and a second quantitative loop are connected at both ends of the third chromatographic column and the second quantitative loop to the ports of the second multi-way valve; a second reference gas and a second carrier gas are respectively connected to the ports of the second multi-way valve; and the ports of the second multi-way valve are connected to the ports of the third multi-way valve.

[0014] A third multi-way valve and a fourth chromatographic column, wherein the two ends of the fourth chromatographic column are respectively connected to the ports of the third multi-way valve, and the ports of the third multi-way valve are connected to the first channel of the TCD.

[0015] Another objective of this invention is to provide a method for measuring hydrogen and non-hydrogen components based on a single TCD, which is achieved through the following technical solution:

[0016] A method for measuring hydrogen and non-hydrogen components based on a single TCD, wherein the method for measuring hydrogen and non-hydrogen components based on a single TCD is as follows:

[0017] When switched to the first state, the sample gas passes through the first and second quantitative loops in sequence. At the same time, the first reference gas passes through the first multi-way valve, the second chromatographic column, and the second channel of the only TCD in sequence. The second reference gas passes through the second and third multi-way valves in sequence and the first channel of the only TCD in sequence. The two ends of the first quantitative loop are connected to the ports of the first multi-way valve, and the two ends of the second quantitative loop are connected to the ports of the second multi-way valve.

[0018] When switching to the second state, the first carrier gas passes sequentially through the first metering loop, the first chromatographic column, the second chromatographic column, and the second channel; the second carrier gas passes sequentially through the second metering loop, the third chromatographic column, the fourth chromatographic column, and the first channel; the two ends of the first chromatographic column are respectively connected to the ports of the first multi-way valve; the two ends of the third chromatographic column and the second metering loop are respectively connected to the ports of the second multi-way valve; and the two ends of the fourth chromatographic column are respectively connected to the ports of the third multi-way valve.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] 1. Simple structure and low cost;

[0021] By utilizing the retention time difference of the components to be analyzed, the two channels of the TCD can be used as reference and measurement channels for each other, thus realizing the measurement of hydrogen and non-hydrogen components with a single TCD.

[0022] 2. Excellent working performance;

[0023] When using a single TCD with different carrier gases (reference and measurement), the measurement-reference method can still reduce the noise of the TCD without changing the TCD response.

[0024] The first reference gas and the first carrier gas are nitrogen or helium, and the second reference gas and the second carrier gas are hydrogen or helium, thus avoiding the additional gas consumption for the TCD detector reference flow path. Attached Figure Description

[0025] The disclosure of this invention will become more readily understood with reference to the accompanying drawings. It will be readily understood by those skilled in the art that these drawings are merely illustrative of the technical solutions of this invention and are not intended to limit the scope of protection of this invention. In the drawings:

[0026] Figure 1 This is a schematic diagram of the hydrogen and non-hydrogen component measurement device based on a single TCD according to an embodiment of the present invention. Detailed Implementation

[0027] Figure 1 The following description illustrates optional embodiments of the invention to teach those skilled in the art how to implement and reproduce the invention. Some conventional aspects have been simplified or omitted to explain the technical solutions of the invention. Those skilled in the art should understand that variations or substitutions derived from these embodiments will be within the scope of the invention. Those skilled in the art should understand that the following features can be combined in various ways to form multiple variations of the invention. Therefore, the invention is not limited to the following optional embodiments, but is defined only by the claims and their equivalents.

[0028] Example 1:

[0029] Figure 1 A schematic diagram of a hydrogen and non-hydrogen component measuring device based on a single TCD according to an embodiment of the present invention is shown, as follows: Figure 1 As shown, the hydrogen and non-hydrogen component measurement device based on a single TCD includes:

[0030] The first multi-way valve 11, the first chromatographic column 31 and the first quantitative loop 21 are respectively connected to the ports of the first multi-way valve 11, and the first reference gas 51 and the first carrier gas 52 are respectively connected to the ports of the first multi-way valve 11.

[0031] The second chromatographic column 32 and the TCD40 are connected. 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 the second channel 42 of the only TCD40.

[0032] The second multi-way valve 12, the third chromatographic column 33, and the second quantitative loop 22 are connected at both ends to the ports of the second multi-way valve 12; the second reference gas 61 and the second carrier gas 62 are respectively connected to the ports of the second multi-way valve 12; and the ports of the second multi-way valve 12 are connected to the ports of the third multi-way valve 13.

[0033] The third multi-way valve 13 and the fourth chromatographic column 34 are connected at both ends to the ports of the third multi-way valve 13, and the ports of the third multi-way valve 13 are connected to the first channel 41 of the TCD 40.

[0034] To ensure accurate switching and flow path connectivity, further, when switching to the first state, the sample gas passes sequentially through the first quantitative loop 21 and the second quantitative loop 22, while the first reference gas 51 passes sequentially through the first multi-way valve 11, the second chromatographic column 32, and the second channel 42, and the second reference gas 61 passes sequentially 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 sequentially through the first quantitative loop 21, the first chromatographic column 31, the second chromatographic column 32, and the second channel 42, while the second carrier gas 62 passes sequentially through the second quantitative loop 22, the third chromatographic column 33, the fourth chromatographic column 34, and the first channel 41.

[0035] To share gases and reduce costs, the first reference gas 51 and the first carrier gas 52 are further made of nitrogen or helium, and the second reference gas 61 and the second carrier gas 62 are made of hydrogen or helium.

[0036] To obtain more information on non-hydrogen components, the single-TCD-based hydrogen and non-hydrogen component measurement device further includes:

[0037] The fifth chromatographic column 35 is connected at one end to the port of the third multi-way valve 13 and at the other end to the first channel 41.

[0038] To improve operational reliability, the first multi-way valve 11, the second multi-way valve 12, and the third multi-way valve 13 are all ten-way valves.

[0039] The method for measuring hydrogen and non-hydrogen components based on a single TCD according to embodiments of the present invention is as follows:

[0040] Switching to the first state, the sample gas passes sequentially through the first quantitative loop 21 and the second quantitative loop 22. Simultaneously, the first reference gas 51 passes sequentially through the first multi-way valve 11, the second chromatographic column 32, and the second channel 42 (hydrogen measurement channel) of the only TCD 40. The second reference gas 61 passes sequentially through the second multi-way valve 12, the third multi-way valve 13, and the first channel 41 (non-hydrogen component measurement channel) of the only TCD 40. The two ends of the first quantitative loop 21 are respectively connected to the ports of the first multi-way valve 11, and the two ends of the second quantitative loop 22 are connected to the ports of the second multi-way valve 12.

[0041] When switching to the second state, the first carrier gas 52 passes sequentially through the first metering ring 21, the first chromatographic column 31, the second chromatographic column 32, and the second channel 42; the second carrier gas 62 passes sequentially through the second metering ring 22, the third chromatographic column 33, the fourth chromatographic column 34, and the first channel 41. The two ends of the first chromatographic column 31 are respectively connected to the ports of the first multi-way valve 11; the two ends of the third chromatographic column 33 and the second metering ring 22 are respectively connected to the ports of the second multi-way valve 12; and the two ends of the fourth chromatographic column 34 are respectively connected to the ports of the third multi-way valve 13.

[0042] To share gases and reduce costs, the first reference gas 51 and the first carrier gas 52 are further made of nitrogen or helium, and the second reference gas 61 and the second carrier gas 62 are made of hydrogen or helium.

[0043] To obtain a higher content of non-hydrogen components, a fifth chromatographic column is further provided, with one end of the fifth chromatographic column connected to the port of the third multi-way valve and the other end connected to the first channel.

[0044] Example 2:

[0045] An application example of the hydrogen and non-hydrogen component measurement device and method based on a single TCD according to Embodiment 1 of the present invention.

[0046] In this application example, such as Figure 1 As shown, the first multi-port valve 11, the second multi-port valve 12, and the third multi-port valve 13 are all ten-port valves; the two ends of the first chromatographic column 31 and the first quantitative loop 21 are respectively connected to the port of the first multi-port valve 11; the first reference gas 51 and the first carrier gas 52 are both nitrogen and are respectively connected to the port of the first multi-port valve 11; there is only one TCD 40, the first channel 41 is the non-hydrogen component measurement channel, which is connected to the port of the third multi-port valve 13 through the fifth chromatographic column 35; the second channel 42 is the hydrogen measurement channel, which is connected to the port of the first multi-port valve 11 through the second chromatographic column 32.

[0047] The two ends of the second quantitative ring 22 and the third chromatographic column 33 are respectively connected to the ports of the second multi-way valve 12. The second reference gas 61 and the second carrier gas 62 are both hydrogen and are respectively connected to the ports of the second multi-way valve 12.

[0048] The two ends of the fourth chromatographic column 34 are connected to the ports of the third multi-way valve 13, and the ports of the third multi-way valve 13 are connected to the ports of the second multi-way valve 12.

[0049] The hydrogen and non-hydrogen component measurement method based on a single TCD in this embodiment of the invention, that is, the working process of the measuring device in this embodiment, is as follows:

[0050] When the three multi-way valves are switched to the first state, the sample gas passes through the first quantitative loop 21 and the second quantitative loop 22 in the forward direction in sequence. At the same time, the first reference gas 51 passes through the first multi-way valve 11, the second chromatographic column 32 and the only second channel 42 (hydrogen measurement channel) of the TCD40 in sequence. The second reference gas 61 passes through the second multi-way valve 12, the third multi-way valve 13, the fifth chromatographic column 35 and the only first channel 41 (non-hydrogen component measurement channel) of the TCD40 in sequence.

[0051] When the three multi-way valves are switched to the second state, the first carrier gas 52 passes through the first metering ring 21 (reverse flow), the first chromatographic column 31, the second chromatographic column 32 and the second channel 42 in sequence, and the second carrier gas 62 passes through the second metering ring 22 (reverse flow), the third chromatographic column 33, the fourth chromatographic column 34, the fifth chromatographic column and the first channel 41 in sequence.

[0052] Example 3:

[0053] The application example of the hydrogen and non-hydrogen component measurement device and method based on a single TCD according to Embodiment 1 of the present invention differs from Embodiment 2 in that:

[0054] The first reference gas 51 and the first carrier gas 52 are both helium, and the second reference gas 61 and the second carrier gas 62 are both helium, that is, the same gas is used.

Claims

1. A single-TCD-based hydrogen and non-hydrogen component measurement device, comprising a first multi-port valve, a first chromatographic column, and a first metering loop, wherein the two ends of the first metering loop and the first chromatographic column are respectively connected to the ports of the first multi-port valve, and a first reference gas and a first carrier gas are respectively connected to the ports of the first multi-port valve; characterized in that, The hydrogen and non-hydrogen component measurement device based on a single TCD also includes: The second chromatographic column and the TCD, one end of the second chromatographic column is connected to the port of the first multi-port valve, and the other end is connected to the second channel of the only TCD; A second multi-way valve, a third chromatographic column, and a second quantitative loop are connected at both ends of the third chromatographic column and the second quantitative loop to the ports of the second multi-way valve; a second reference gas and a second carrier gas are respectively connected to the ports of the second multi-way valve; and the ports of the second multi-way valve are connected to the ports of the third multi-way valve. A third multi-way valve and a fourth chromatographic column, wherein the two ends of the fourth chromatographic column are respectively connected to the ports of the third multi-way valve, and the ports of the third multi-way valve are connected to the first channel of the TCD.

2. The hydrogen and non-hydrogen component measuring device based on a single TCD according to claim 1, characterized in that, When switched to the first state, the sample gas passes through the first and second quantitative loops in sequence, while the first reference gas passes through the first multi-way valve, the second chromatographic column, and the second channel in sequence, and the second reference gas passes through the second multi-way valve, the third multi-way valve, and the first channel in sequence. When switched to the second state, the first carrier gas passes through the first quantitative loop, the first chromatographic column, the second chromatographic column, and the second channel in sequence, and the second carrier gas passes through the second quantitative loop, the third chromatographic column, the fourth chromatographic column, and the first channel in sequence.

3. The hydrogen and non-hydrogen component measuring device based on a single TCD according to claim 2, characterized in that, The first reference gas and the first carrier gas are nitrogen or helium, and the second reference gas and the second carrier gas are hydrogen or helium.

4. The hydrogen and non-hydrogen component measuring device based on a single TCD according to claim 1, characterized in that, The hydrogen and non-hydrogen component measurement device based on a single TCD also includes: The fifth chromatographic column has one end connected to the port of the third multi-way valve and the other end connected to the first channel.

5. The hydrogen and non-hydrogen component measuring device based on a single TCD according to claim 1, characterized in that, The first multi-way valve, the second multi-way valve, and the third multi-way valve are all ten-way valves.

6. The method for measuring hydrogen and non-hydrogen components based on a single TCD implemented by the measuring device according to claim 1, wherein the method for measuring hydrogen and non-hydrogen components based on a single TCD is as follows: When switched to the first state, the sample gas passes through the first and second quantitative loops in sequence. At the same time, the first reference gas passes through the first multi-way valve, the second chromatographic column, and the second channel of the only TCD in sequence. The second reference gas passes through the second and third multi-way valves in sequence and the first channel of the only TCD in sequence. The two ends of the first quantitative loop are connected to the ports of the first multi-way valve, and the two ends of the second quantitative loop are connected to the ports of the second multi-way valve. When switching to the second state, the first carrier gas passes sequentially through the first metering loop, the first chromatographic column, the second chromatographic column, and the second channel; the second carrier gas passes sequentially through the second metering loop, the third chromatographic column, the fourth chromatographic column, and the first channel; the two ends of the first chromatographic column are respectively connected to the ports of the first multi-way valve; the two ends of the third chromatographic column and the second metering loop are respectively connected to the ports of the second multi-way valve; and the two ends of the fourth chromatographic column are respectively connected to the ports of the third multi-way valve.

7. The method for measuring hydrogen and non-hydrogen components based on a single TCD according to claim 6, characterized in that, The first reference gas and the first carrier gas are nitrogen or helium, and the second reference gas and the second carrier gas are hydrogen or helium.

8. The method for measuring hydrogen and non-hydrogen components based on a single TCD according to claim 6, characterized in that, A fifth chromatographic column is also provided, with one end of the fifth chromatographic column connected to the port of the third multi-way valve and the other end connected to the first channel.

9. The method for measuring hydrogen and non-hydrogen components based on a single TCD according to claim 6, characterized in that, The first channel is a non-hydrogen component measurement channel, and the second channel is a hydrogen measurement channel.

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