CN115856179A - Automatic gas chromatography measuring system for dissolved greenhouse gas - Google Patents
Automatic gas chromatography measuring system for dissolved greenhouse gas Download PDFInfo
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- CN115856179A CN115856179A CN202211622833.2A CN202211622833A CN115856179A CN 115856179 A CN115856179 A CN 115856179A CN 202211622833 A CN202211622833 A CN 202211622833A CN 115856179 A CN115856179 A CN 115856179A
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Abstract
The invention discloses an automatic gas chromatography determination system for dissolved greenhouse gas, which comprises a headspace bottle filled with a sample to be determined, a three-way electromagnetic valve, a peristaltic pump, a quantitative ring for controlling air inflow, a six-way two-position switching valve, a stainless steel packed column with PorapakQ filler and a gas chromatograph equipped with a hydrogen flame ionization detector; one end of a sample inlet needle head is inserted into a rubber plug of a headspace bottle of a sample to be detected and is positioned above water in the headspace bottle, a long needle head is arranged in the headspace bottle, one end of the long needle head is contacted with the bottom in the headspace bottle, the other end of the long needle head extends out of the headspace bottle and is connected with one end of a peristaltic pump, the other end of the peristaltic pump is communicated with a bottle filled with water through a hose, and the water is pumped into the headspace bottle through the peristaltic pump; the other end of the sample inlet needle is provided with a three-way electromagnetic valve, and the other end of the three-way electromagnetic valve is communicated with the sixth channel port. The invention can realize the continuous automatic sample introduction and measurement of the sample by operating special software, and converts the signal of the detector into a chromatogram for qualitative and quantitative analysis.
Description
Technical Field
The invention belongs to the field of analysis technology test, and particularly relates to an automatic gas chromatography measuring system for dissolved greenhouse gases.
Background
An existing dissolved greenhouse gas measuring system is shown in figure 1, when a sample is measured, V1 and V2 are in a sampling state (a solid line gas path), carrier gas directly passes through a chromatographic column, firstly, V3 is adjusted to introduce high-purity nitrogen, a V4 valve is adjusted to lead (1) - (2) to be introduced, and a sample introduction gas path and a quantitative ring are flushed by the high-purity nitrogen for 60s, so that the sample introduction gas path is not interfered by a previous sample. After the washing is stopped, V4 is adjusted to communicate (2) - (3), and V5 is closed. Because the amount of head space balance gas (sample gas) is relatively small to achieve dissolved CH 4 And N 2 The O reaches equilibrium as soon as possible and ensures that the concentration is high enough to facilitate the determination. Therefore, the tail end of the sample injection gas circuit is provided with a micro vacuum pump part, and the gas circuit from the V5 valve to the vacuum pump section is pumped to negative pressure (about 600 hpa) so as to reduce the headspace gas consumed by gas circuit flushing as much as possible and ensure the measurement requirement. Gas circuit middle distributionThe digital display pressure gauge can display the pressure in the gas circuit in real time and monitor whether the gas circuit leaks gas or not. Then prick the syringe needle of the sample inlet into the rubber stopper of the headspace bottle, open V5 while the vacuum pump is stopped, prevent the environmental gas from flowing back into the gas path from the air outlet of the vacuum pump, and inject the discharged water sample back into the bottle with the syringe as soon as possible, "force" the headspace gas to enter the gas path, finish the washing and sampling of the quantitative loop (loop 1 and loop 2). And starting a measurement command when the digital display pressure gauge displays that the pressure in the gas path is stable, namely no air flow pulse exists in the sample injection gas path and the pressure is the same as the ambient atmospheric pressure. The system chemical workstation automatically switches V1 and V2 to a 'sample introduction' state (a dotted line gas path), high-purity nitrogen and argon-methane carrier gas respectively carry gas samples in loop2 and loop1 into a chromatographic column and complete separation, and finally respectively enter FID and mu ECD to synchronously complete CH 4 And N 2 Measurement of O and signal output. Wherein, in the channel of μ ECD, in N 2 After the O passes through the column C1, V1 automatically switches back to the "sample" state. At the moment, high-purity nitrogen in the AUX2 path can blow out components such as water vapor with long retention time in the C1 from the reverse direction. The process can shorten the sample analysis time and prolong the service life of the chromatographic column.
Above-mentioned dissolve greenhouse gas survey system's gas chromatography system data acquisition inefficiency, survey the appearance in-process and need artifical manual operation to accomplish operations such as gas circuit washing, appearance and valve switching, can consume more time and human cost, the technical threshold height, and can't realize the automatic continuity survey of sample, precision when survey dissolve greenhouse gas also can receive certain jamming.
The Agilent7697A headspace auto-sampler currently on the market, as shown in fig. 2, is based on the Agilent 7890GC and 7693A auto-liquid sampler architecture design. It provides an inert sample channel, can avoid analyte degradation or loss, realizes outstanding gas chromatography performance, improves efficiency by a wide margin, provides reliable and stable introduction technique simultaneously to ensure the integrality of advancing a kind at every turn. Automatic leak detection ensures that each sample bottle has no leak before analysis, and precision or sensitivity is not lost. Hydrogen can be safely used as a substitute carrier gas. Important samples that arrive late can be analyzed in time using the priority sample location function. The air pressure compensation function may ensure that more accurate, consistent results are obtained in multiple laboratories. The sample bottles are generally configured to have a small capacity of 10mL and 20 mL. But the commercial instrument is expensive, has small single sample volume, is mostly used for analyzing trace or trace substances assembled with a capillary chromatographic column, and is not suitable for analyzing dissolved greenhouse gases.
To sum up, the artifical manual sample introduction that adopts among the greenhouse gas analysis, every survey a sample and all must artifical manual operation syringe to realize advancing the kind survey at the survey appearance in-process, the continuity survey of sample can not be realized to this kind of determine mode, because it advances the kind to be artifical manual, precision when consequently survey dissolving greenhouse gas also can receive certain artificial interference, and this system can consume more manual works and time cost when the sample is surveyed, can't satisfy present high accuracy and convenient and fast's survey demand, can't agree with the observation technique development and the tendency of increasing the sophistication at home and abroad gradually. Although a complete set of headspace automatic sample injectors exist at present, the instrument is expensive, has small single sample injection amount, is mostly used for analyzing volatile substances in samples, and is not suitable for analyzing dissolved greenhouse gases.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides an automatic gas chromatography determination system for dissolved greenhouse gas, and the automatic gas chromatography determination system is obtained by modifying a gas chromatograph ， And the device is combined with a headspace balance automatic sampling device which is designed and integrated autonomously, so as to establish a gas chromatography system which is suitable for the automatic, high-precision and high-accuracy online continuous observation of dissolved greenhouse gases.
The technical scheme adopted by the invention is as follows:
an automatic gas chromatography measuring system for dissolved greenhouse gas is characterized by comprising a headspace bottle filled with a sample to be measured, a three-way electromagnetic valve, a peristaltic pump, a quantitative ring for controlling air inflow, a six-way two-position switching valve, a stainless steel packed column and a gas chromatograph equipped with a hydrogen flame ionization detector; the six-way double-position switching valve is provided with a first channel port, a second channel port, a third channel port, a fourth channel port, a fifth channel port and a sixth channel port, the quantitative ring is connected between the first channel port and the fourth channel port, the stainless steel filling column is connected between the third channel port and the hydrogen flame ionization detector, and the hydrogen flame ionization detector is connected with a converter;
one end of a sample inlet needle head is inserted into a rubber plug of a headspace bottle of the sample to be detected and is positioned above water in the headspace bottle, a long needle head is arranged in the headspace bottle, one end of the long needle head is contacted with the bottom in the headspace bottle, the other end of the long needle head extends out of the headspace bottle and is connected with one end of a peristaltic pump, the other end of the peristaltic pump is communicated with a bottle filled with water through a hose, and the water is pumped into the headspace bottle through the peristaltic pump;
the other end of the sample inlet needle is provided with the three-way electromagnetic valve, the other end of the three-way electromagnetic valve is communicated with the sixth channel port, the sixth channel port forms a sample gas inlet, and the third channel port is connected with the greenhouse gas standard gas.
Further, the second passage opening constitutes a carrier gas inlet opening.
Furthermore, the inlet end of the hydrogen flame ionization detector is respectively connected with an air generator and a hydrogen generator.
Further, the reformer is a nickel reformer for converting incombustible CO 2 And CO is converted to CH over a nickel catalyst at high temperature 4。
Furthermore, the filler of the stainless steel packed column is PorapakQ 。
Compared with the prior art, the invention has the beneficial effects that:
the invention is modified based on the prior art, a gas chromatograph is connected with a PC, and the AgilentChemStation (Agilent chemical workstation) is used as data analysis system software commonly used in the field. The software is networked with a gas chromatograph, a peristaltic pump (V2) mentioned in figure 3 can be added in a valve configuration block on the software, a three-way electromagnetic valve (V3), a six-way two-position switching valve (V4), after the setting, running events of all valves (such as the switching time of all valves) can be set again, a sample injection sequence table is set, then the set sequence can be operated on a computer to realize continuous automatic sample injection determination of samples, detector signals are converted into chromatograms to carry out qualitative and quantitative analysis, the precision and the reproducibility of an analysis system are improved, errors caused by manual sample injection are avoided, the sample measurement time and the running cost are saved, the capacity of detecting dissolved greenhouse gases by automatic sample injection is realized, further, the online high-precision automatic monitoring experiment of the dissolved greenhouse gases is realized, the running is more stable, the running cost is lower, the operation is simpler, and the requirements of the current dissolved greenhouse gases can be met in all aspects.
Drawings
FIG. 1 is a schematic diagram of a conventional dissolved greenhouse gas measurement system.
FIG. 2 is a schematic diagram of a conventional Agilent7697A headspace auto-sampler as a whole.
FIG. 3 is a schematic diagram of an automatic dissolved greenhouse gas measurement system according to the present invention.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration and explanation only, not limitation.
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The invention will be described in detail below with reference to exemplary embodiments and with reference to the accompanying drawings.
Referring to fig. 3, the automatic gas chromatography system for dissolved greenhouse gas of the present invention comprises a headspace bottle 1 containing a sample to be measured, a three-way solenoid valve 2, a peristaltic pump, a quantitative ring 4 for controlling air inflow, a six-way two-position switching valve 5, a stainless steel packed column 6, and a gas chromatograph equipped with a hydrogen flame ionization detector 7; the six-way two-position switching valve 5 is provided with a first channel port 51, a second channel port 52, a third channel port 53, a fourth channel port 54, a fifth channel port 55 and a sixth channel port 56, the quantitative ring 4 is connected between the first channel port 51 and the fourth channel port 54, the stainless steel packed column 6 is connected between the third channel port 53 and the hydrogen flame ionization detector 7, and the hydrogen flame ionization detector 7 is connected with a converter;
one end of a sample inlet needle head is inserted into a rubber plug of a headspace bottle 1 of the sample to be detected and is positioned above water in the headspace bottle, a long needle head is arranged in the headspace bottle 1, one end of the long needle head is contacted with the bottom in the headspace bottle 1, the other end of the long needle head extends out of the headspace bottle 1 and is connected with one end of a peristaltic pump, the other end of the peristaltic pump is communicated with a bottle 3 filled with water through a hose, and the water is pumped into the headspace bottle 1 through the peristaltic pump;
the other end of the sample inlet needle is provided with the three-way electromagnetic valve 2, the other end of the three-way electromagnetic valve 2 is communicated with the sixth channel port 56, the sixth channel port 56 forms a sample gas inlet, and the third channel port 53 is connected with the greenhouse gas standard gas 11. Specifically, when the sample is injected, the three-way electromagnetic valve 2 (1) - (2) is open and is communicated with the sixth channel port 56 through the three-way electromagnetic valve 2 (1) - (2), and when the standard greenhouse gas 11 is injected, the three-way electromagnetic valve 2 (2) - (3) is open, and at this time, the standard greenhouse gas 11 is communicated with the sixth channel port 56 through the three-way electromagnetic valve 2 (2) - (3). When the sample is fed, the carrier gas 8 finally enters the stainless steel packed column 6 through the third channel port 53 by the co-carrier gas to be detected to complete the separation.
Further, the second port 52 constitutes a carrier gas inlet port.
Further, the inlet ends of the hydrogen flame ionization detector 7 are respectively connected with an air generator 9 and a hydrogen generator 10.
Further, the reformer is a nickel reformer for converting incombustible CO 2 And CO is converted into CH at high temperature by a nickel catalyst 4 。
Furthermore, the filler of the stainless steel packed column 6 is Porapak Q.
The specific process of the invention is as follows:
in sample measurement, as shown in fig. 3, V4 is in "sampling" state (solid gas path), and carrier gas (high purity nitrogen, purity better than 99.999%) is directly passed through the chromatographic column. Firstly, a syringe needle of a sample inlet is pricked into a rubber plug of a headspace bottle of a sample to be detectedAdjusting a V3 valve to ventilate (1) - (2), connecting a long needle in a headspace bottle to one end of a peristaltic pump, connecting the other end of the peristaltic pump to a bottle filled with water by using a hose, opening the V2 valve, pumping the water in the bottle filled with water into the headspace bottle by using the peristaltic pump (the working time of the peristaltic pump can be set according to the volume of a sample), and 'forcing' headspace gas to enter an air path from the (1) - (2) to finish the flushing and sampling of a quantitative ring (Loop). When the digital display pressure gauge displays that the pressure in the gas path is stable, the pressure gauge is positioned in the gas chromatograph, and the corresponding gas path pressure can be seen on a control panel on the gas chromatograph, namely, no air flow pulse exists in the sample injection gas path, and the pressure is the same as the ambient atmospheric pressure, and a determination command is started. The chemical workstation of the system automatically switches V4 to a sample introduction state (a dotted line gas path), high-purity nitrogen brings a gas sample in Loop into a chromatographic column and completes separation, and finally enters FID to complete CH 4 And (4) measurement and signal output.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise explicitly stated or limited, the terms "mounted," "connected," "fixed," and the like are to be construed broadly, e.g., as being permanently connected, detachably connected, or integral; may be mechanically coupled, may be electrically coupled or may be in communication with each other; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
In the present invention, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may be directly contacting the second feature or the first and second features may be indirectly contacting each other through intervening media. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (5)
1. An automatic gas chromatography measuring system for dissolved greenhouse gas is characterized by comprising a headspace bottle filled with a sample to be measured, a three-way electromagnetic valve, a peristaltic pump, a quantitative ring for controlling air inflow, a six-way two-position switching valve, a stainless steel packed column and a gas chromatograph equipped with a hydrogen flame ionization detector; the six-way double-position switching valve is provided with a first channel port, a second channel port, a third channel port, a fourth channel port, a fifth channel port and a sixth channel port, the quantitative ring is connected between the first channel port and the fourth channel port, the stainless steel filling column is connected between the third channel port and the hydrogen flame ionization detector, and the hydrogen flame ionization detector is connected with a converter;
one end of a sample inlet needle is inserted on a rubber plug of a headspace bottle of the sample to be detected and is positioned above water in the headspace bottle, a long needle is arranged in the headspace bottle, one end of the long needle is contacted with the bottom in the headspace bottle, the other end of the long needle extends out of the headspace bottle and is connected with one end of a peristaltic pump, the other end of the peristaltic pump is communicated with a bottle filled with water through a hose, and the water is pumped into the headspace bottle through the peristaltic pump;
the other end of the sample inlet needle is provided with the three-way electromagnetic valve, the other end of the three-way electromagnetic valve is communicated with the sixth channel port, the sixth channel port forms a sample gas inlet, and the third channel port is connected with the greenhouse gas standard gas.
2. A dissolved greenhouse gas automated gas chromatography assay as claimed in claim 1 in which the second port forms a carrier gas inlet.
3. The automated gas chromatography assay system for greenhouse gases in dissolved state as claimed in claim 2 or 3, wherein the inlet end of said hydrogen flame ionization detector is connected with an air generator and a hydrogen generator respectively.
4. The automated gas chromatography assay system for greenhouse gases in dissolved form as claimed in claim 3 wherein said reformer is a nickel reformer for converting incombustible CO 2 And CO is converted to CH over a nickel catalyst at high temperature 4 。
5. The automated gas chromatography assay system for greenhouse gases in dissolved form as claimed in claim 4, wherein the packing of said stainless steel packed column is PorapakQ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211622833.2A CN115856179A (en) | 2022-12-16 | 2022-12-16 | Automatic gas chromatography measuring system for dissolved greenhouse gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211622833.2A CN115856179A (en) | 2022-12-16 | 2022-12-16 | Automatic gas chromatography measuring system for dissolved greenhouse gas |
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| CN115856179A true CN115856179A (en) | 2023-03-28 |
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| CN202211622833.2A Pending CN115856179A (en) | 2022-12-16 | 2022-12-16 | Automatic gas chromatography measuring system for dissolved greenhouse gas |
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- 2022-12-16 CN CN202211622833.2A patent/CN115856179A/en active Pending
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