CN111044664A - Gas chromatography detection device based on dielectric barrier discharge emission spectrum - Google Patents
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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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- 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
- G01N30/70—Electron capture detectors
-
- 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
- G01N30/74—Optical detectors
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Abstract
The invention discloses a gas chromatography detection device based on dielectric barrier discharge emission spectrum, which comprises a gas chromatograph and a dielectric barrier discharge device, wherein the outlet of the dielectric barrier discharge device is connected with a CCD (charge coupled device) detector through an optical fiber, a quartz tube is arranged in the dielectric barrier discharge device, a metal electrode is wound on the upper part of the quartz tube, the lower part of the quartz tube is provided with a metal tube metal electrode which is away from the metal tube by a set distance, the metal electrode and one end of the metal tube, which is far away from the quartz tube, are both connected with a high-voltage power supply device, and the metal tube is connected with a sample outlet of the gas chromatograph. According to the invention, DBD-OES is used as a multi-channel and element-specific GC detector to measure volatile sulfur-containing and nitrogen-containing organic compounds and inorganic compounds, so that the instrument and analysis cost is remarkably reduced, and the defects of the GC detector of the traditional atomic spectrometer are overcome.
Description
Technical Field
The invention relates to the technical field of spectral analysis, in particular to a detection device based on the combination of dielectric barrier discharge emission spectrum and gas chromatography.
Background
The innovation of detectors in the development process of gas chromatographs is a main factor driving the gas chromatographs, and as for common gas chromatographic detectors, thermal conductivity detectors, hydrogen flame ionization detectors, electron capture detectors and flame photometric detectors have obvious limitations and selectivity. The thermal conductivity detector and the hydrogen flame ionization detector are general-purpose detectors, but the thermal conductivity detector has low sensitivity. The hydrogen flame ionization detector is suitable for analyzing trace organic matters in water and atmosphere or organic matters polluted by oxides of water, N and S, and basically has no response to other substances. The electron capture detector responds primarily to compounds containing atoms with greater electronegativity. The flame photometric detector has high selectivity and high sensitivity to sulfur-phosphorus-containing organic compounds.
Dielectric Barrier Discharge (DBD) is a low temperature plasma, a reliable atomic emission spectroscopy (OES) excitation source, can be operated at atmospheric pressure with low power consumption and low gas consumption, and can be used in convenient instruments for field analysis. Besides being used for detecting heavy metals, DBDs have been used for detecting small molecule gases such as ammonia, hydrogen sulfide, nitric oxide, and the like. At present, a path of carrier gas is required to be added additionally for the combination of GC and DBD-OES to enable the DBD to continuously generate micro-plasma, so that GC effluent and the carrier gas are mixed together and then enter the DBD-OES, and a large amount of dilution is caused, and the detection sensitivity is low.
Disclosure of Invention
The invention aims to provide a gas chromatography detection device based on dielectric barrier discharge emission spectroscopy, and develops the gas chromatography detection device into a gas chromatography detection method with high selectivity, high stability and high sensitivity on nitrogen and sulfur, and the gas chromatography detection device is used for gas chromatography detection of nitrogen and sulfur compounds.
The utility model provides a gas chromatography detection device based on dielectric barrier discharge emission spectrum, includes gas chromatograph and dielectric barrier discharge device, there is the CCD detector dielectric barrier discharge device's export through fiber connection, be provided with the quartz capsule in the dielectric barrier discharge device, the winding of quartz capsule upper portion has metal electrode, the quartz capsule lower part is provided with the metal tube, set for the distance at a distance between metal electrode and the metal tube, the metal electrode all is connected with high voltage power supply unit with the one end that the quartz capsule was kept away from to the metal tube, the metal tube is connected with gas chromatograph's appearance mouth.
Preferably, the high voltage power supply device comprises a contact voltage regulator and a neon lamp power supply.
Preferably, the output end of the contact voltage regulator is connected with the input end of a neon lamp power supply, and the output end of the neon lamp power supply is respectively connected with the metal tube and the metal electrode.
Preferably, the contact voltage regulator is an adjustable autotransformer.
Preferably, the optical fiber comprises an optical fiber probe, and a perspective window is arranged at the front end of the optical fiber probe.
Preferably, the center of the quartz tube 3 is perpendicular to the fiber probe 8.
Preferably, the metal tube is inserted into the quartz tube.
Preferably, the metal tube is a stainless steel tube, and the metal electrode is a copper wire.
Preferably, the quartz tube is 50mm long, 1.6mm in inner diameter and 3mm in outer diameter.
Preferably, the dielectric barrier discharge gas is a carrier gas of a gas chromatograph, and the pressure of the carrier gas is 0.1 MPa.
The invention has the beneficial effects that:
(1) according to the invention, DBD-OES is used as a multi-channel and element-specific GC detector to measure volatile sulfur-containing and nitrogen-containing organic compounds and inorganic compounds, so that the instrument and analysis cost is remarkably reduced, and the defects of the GC detector of the traditional atomic spectrometer are overcome.
(2) According to the gas chromatography detection device based on the dielectric barrier discharge atomic emission spectroscopy, the capillary column is inserted into the stainless steel tube, the stainless steel tube is inserted into the quartz tube, and the stainless steel tube directly enters the plasma discharge area through the stainless steel tube interface, so that the dead volume and the dead time are greatly reduced, and the plasma does not need additional carrier gas.
(3) The invention can measure the malodorous gas in the environment, can simultaneously measure organic matters and inorganic matters containing nitrogen and sulfur, and can be particularly used for methyl mercaptan, ethyl mercaptan, methyl sulfide, dimethyl disulfide, hydrogen sulfide, trimethylamine and other compounds, and the detection effect of the invention is similar to that of a flame photometric detector and an electronic capture detector.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of the overall structure of the present invention;
FIG. 2 is a schematic diagram of the connection of a high voltage power supply to a stainless steel tube and a metal electrode;
in fig. 1 to 2, 1 is a gas chromatography sample inlet, 2 is a metal tube, 3 is a quartz tube, 4 is a metal electrode, 5 is a CCD detector, 6 is a gas chromatograph, 7 is a dielectric barrier discharge device, 8 is an optical fiber probe, 9 is a neon lamp power supply, and 10 is a contact voltage regulator.
FIG. 3 is a characteristic spectrum of 0.04 ④ L of dimethyl disulfide produced in the present apparatus system;
FIG. 4 is a characteristic spectrum of 0.02 ④ L of thiomethyl ether produced in the present apparatus system;
FIG. 5 is a characteristic spectrum of 0.04 ④ L of ethanethiol generated with the present device system;
FIG. 6 is a characteristic spectrum diagram of 1mL hydrogen sulfide gas generated under the system of the device;
FIG. 7 is a characteristic spectrum of 0.04 ④ L of methyl mercaptan generated in the present apparatus system;
FIG. 8 is a characteristic spectrum of 0.10 ④ L of trimethylamine produced in the present apparatus system;
FIG. 9 is a graph of the signal strength of 0.06 ④ L of dimethyldisulfide at different voltages;
FIG. 10 is a graph of signal intensity for 1.00mL of hydrogen sulfide gas at different voltages;
FIG. 11 is a graph of the signal intensity of 0.10 ④ L trimethylamine solution at different voltages.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present application without making any creative effort, shall fall within the protection scope of the present application.
In the description of the present invention, it is to be understood that the terms "center", "length", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "axial", "radial", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present 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 implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In the description of the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "fixed" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral part; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Fig. 1 is a schematic structural diagram of an embodiment of the present invention, including: a gas chromatograph 6 and a detector. The detector comprises: a dielectric barrier discharge device 7 and a CCD detection device 5; a quartz tube 3 is arranged in the dielectric barrier discharge device 7, a metal tube 2 is inserted in the lower part of the quartz tube 3, the metal tube is a stainless steel tube, a metal electrode 4 is wound on the upper part of the quartz tube 3, the metal electrode is a copper wire, and a gas chromatography sample injection needle is inserted into a sample injection port 1 of a gas chromatograph 6; the sample outlet of the gas chromatograph 6 is connected with a stainless steel tube of the dielectric barrier discharge device 7, the analyte flows out of the capillary chromatographic column and enters the dielectric barrier discharge micro-plasma for excitation, and the outlet of the dielectric barrier discharge is connected with the CCD detection device 5 through the optical fiber probe 8. The outlet end of the quartz tube 3 and the optical fiber probe 8 are arranged in an angle of 180 degrees.
Specifically, the dielectric barrier discharge device 7 includes: a metal tube 2, a quartz tube 3, a metal electrode 4, a high-voltage power supply device; one end of the stainless steel tube 2 is connected with the outlet of the capillary tube, and the other end of the stainless steel tube is inserted into the quartz tube; the metal electrode 4 is wound on the outer wall of the quartz tube 3; and a preset distance is reserved between the stainless steel pipe 2 and the metal electrode 4, and the tail ends of the stainless steel pipe and the metal electrode are respectively connected with the output end of the high-voltage power supply device.
In this embodiment, a transparent window is arranged at the front end of the optical fiber probe 8 of the CCD detector 5, and the transparent window is made of quartz high-temperature resistant transparent material so as to collect signals and protect the optical fiber probe 8; the center of the quartz tube 3 is vertical to the optical fiber probe 8, and the other end of the optical fiber is connected with the CCD detection device 5; the metal electrode 4 is made of copper.
In this embodiment, the high voltage power supply device includes: a contact voltage regulator 10 and a neon power supply 9; the output end of the contact voltage regulator 10 is connected with the input end of a neon lamp power supply 9, the output end of the neon lamp power supply 9 is respectively connected with the tail ends of a stainless steel tube 2 and a metal electrode 4, the contact voltage regulator 10 belongs to an adjustable autotransformer structure and is used for regulating voltage, and the principle is as follows: the coil is uniformly wound on the annular iron core, the electric brush is closely matched and contacted with the polished surface of the coil wire under the pressure of the spring, the electric brush is driven by the rotating shaft to slide on the surface of the coil, the contact position of the electric brush is changed, namely the ratio of the primary turns to the secondary turns of the transformer is changed, so that the output voltage can be smoothly and steplessly regulated within a voltage regulation range, and the input voltage is 220V. The neon transformer is used for obtaining high voltage, and fig. 2 is a schematic diagram of the connection between a contact voltage regulator 10 and a neon power supply 9 and a stainless steel tube and a metal electrode.
In this embodiment, one end of the stainless steel tube 2 is connected to the capillary column outlet, and the other end is inserted into the quartz tube 3; the discharge gas is carrier gas at the outlet of a capillary column of a gas chromatograph, and high-purity argon is used; the analytes from the sample outlet of the gas chromatograph directly enter the dielectric barrier discharge device along with the carrier gas, so that the sensitivity and the analysis efficiency of the device are improved.
In this embodiment, the carrier gas pressure in the gas chromatograph is 0.1 MPa; the output voltage of the high-voltage power supply device is 0.2 kV; the predetermined spacing between the stainless steel tube and the metal electrode is 20 mm.
The working principle of the device is further explained below by taking a specific experiment as an example, and the experimental effect of the device is verified;
the first embodiment is as follows:
the method comprises the specific operation steps of (1) setting the experimental parameters of gas chromatography to be that the gasification temperature is 150 ℃, the injection port temperature is 150 ℃ and the carrier gas pressure is 0.10MPa, (2) opening a high-voltage power supply device, controlling the voltage of an inner electrode and an outer electrode of a DBD device to be 100V by rotating a contact voltage regulator, and continuously and stably generating dielectric barrier discharge micro-plasma, (3) after the chromatographic conditions are stable, sucking a 0.02 ④ L sample by using a 1 ④ L micro-sample injector from the injection port of a gas chromatograph into a chromatographic column, enabling the gas sample separated by the chromatographic column to enter the plasma from an injection port through a stainless steel tube under the action of carrier gas, and (4) after the sample is excited by the plasma, generating a characteristic emission line, detecting the characteristic emission line through a charge coupling device, and quantitatively analyzing the compound, wherein the analyzed compound comprises methyl mercaptan, ethyl mercaptan, methyl sulfide, dimethyl disulfide, hydrogen sulfide, trimethylamine and the like, and the characteristic emission line is shown in figures 3-8.
The device is used for detecting the feasibility of volatile organic sulfide:
first, solutions of dimethyl disulfide, methyl sulfide, ethanethiol, hydrogen sulfide, methyl mercaptan and trimethylamine were measured, respectively, and the results are shown in FIGS. 3 to 8. Taking dimethyl disulfide as an example, as can be seen from fig. 3, the characteristic emission lines 385.13nm, 394.68nm and 420.54nm of dimethyl disulfide can be clearly distinguished from a net signal obtained by subtracting an argon background spectrum signal from a standard solution signal. Similarly, from FIGS. 4-8, it can be concluded that the characteristic emission line of thiomethyl ether is 386.38 nm; the characteristic emission line of ethanethiol is 385.12 nm; the characteristic emission line of methyl mercaptan is 387.65 nm; the characteristic emission lines of the hydrogen sulfide are 387.29nm, 422.96nm and 451.87 nm; the characteristic emission line of trimethylamine is 387.93 nm.
This experiment investigated the effect of discharge voltage on the sensitivity of the device. The optimal conditions of carrier gas pressure of 0.1MPa, electrode distance of 20mm, gasification temperature of 150 ℃ and column temperature of 150 ℃ are respectively selected for carrying out sensitivity test. As shown in FIGS. 9-11, under the optimal conditions, the signal intensities of the three solutions of methyl sulfide, hydrogen sulfide and trimethylamine under different voltages are selected, and the analysis lines are 394.68nm, 387.29nm and 387.93nm respectively. FIG. 9 is a graph showing the change in signal at 85V to 125V for 0.06mL of dimethyldisulfide; FIG. 10 is a graph showing the signal change of 1.00mL of hydrogen sulfide gas at 75V to 125V; FIG. 11 is a graph showing the change in signal from 75V to 125V for 0.10mL of trimethylamine.
Example two:
this example examines the influence of the voltage of the inner and outer electrodes of the DBD on the detection sensitivity of the compound. Referring to the operation procedure of example one, methyl mercaptan, ethyl mercaptan, methyl sulfide, dimethyl disulfide, hydrogen sulfide, and trimethylamine were used as test objects, and the test range of the internal and external electrode voltages was 50V to 125V. Finally, the optimal excitation voltage is determined to be 100V-125V.
Example three:
this example examines the influence of the carrier gas pressure on the compound detection sensitivity in the DBD device. Referring to the procedure of example I, methyl mercaptan, ethyl mercaptan, methyl sulfide, dimethyl disulfide, hydrogen sulfide, and trimethylamine were used as test objects, and the test range of the carrier gas pressure was 0.02MPa to 0.20 MPa. The optimum carrier gas pressure finally determined was 0.10 MPa.
Example four:
this example examines the influence of the inner diameter of a quartz tube on the detection sensitivity of a compound in a DBD device. Referring to the operation procedures of example one, different sizes of quartz tubes were selected for testing, with methyl mercaptan, ethyl mercaptan, methyl sulfide, dimethyl disulfide, hydrogen sulfide, and trimethylamine as the test objects. Finally, the optimal quartz tube size is determined to be 1.6mm in inner diameter and 3.0mm in outer diameter.
Example five:
this example examines the influence of the distance between the stainless steel tube and the metal electrode in the DBD device on the compound detection sensitivity. Referring to the procedure of example one, methyl mercaptan, ethyl mercaptan, methyl sulfide, dimethyl disulfide, hydrogen sulfide, and trimethylamine were used as test objects, the test range of the distance between the stainless steel tube and the metal electrode was 10mm to 25mm, and the finally determined optimum distance was 20 mm.
Under the optimized experimental conditions, the detection sensitivity of the methyl mercaptan, the ethyl mercaptan, the methyl sulfide, the dimethyl disulfide, the hydrogen sulfide and the trimethylamine measured by the method reaches microgram level.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the modifications or substitutions within the scope of the present invention, and shall be covered by the scope of the present invention.
Claims (10)
1. The utility model provides a gas chromatography detection device based on dielectric barrier discharge emission spectrum, its characterized in that, includes gas chromatograph (6) and dielectric barrier discharge device (7), there is CCD detector (5) in dielectric barrier discharge device's the export through optical fiber connection, be provided with quartz capsule (3) in the dielectric barrier discharge device, the winding of quartz capsule upper portion has metal electrode, the quartz capsule lower part is provided with metal tube (2) set distance apart between metal electrode and the metal tube, the one end that quartz capsule was kept away from to metal electrode and metal tube all is connected with high voltage power supply unit, the metal tube is connected with gas chromatograph's appearance mouth.
2. The gas chromatography detection device based on dielectric barrier discharge emission spectrum as claimed in claim 1, characterized in that the high voltage power supply device comprises a contact voltage regulator (10) and a neon lamp power supply (9).
3. The gas chromatography detection device based on dielectric barrier discharge emission spectrum according to claim 2, wherein the output end of the contact voltage regulator is connected with the input end of a neon lamp power supply, and the output end of the neon lamp power supply is respectively connected with the metal tube and the metal electrode.
4. The gas chromatography detection device based on dielectric barrier discharge emission spectroscopy as claimed in claim 1, wherein said contact voltage regulator (10) is a variable autotransformer.
5. The gas chromatography detection device based on dielectric barrier discharge emission spectroscopy as claimed in claim 1, wherein the optical fiber comprises an optical fiber probe (8), and a transparent window is arranged at the front end of the optical fiber probe.
6. The gas chromatography detection device based on dielectric barrier discharge emission spectroscopy as claimed in claim 1, wherein the center of the quartz tube 3 is perpendicular to the center of the optical fiber probe 8.
7. The gas chromatography detection apparatus based on dielectric barrier discharge emission spectroscopy as claimed in claim 1, wherein the metal tube is inserted into a quartz tube.
8. The gas chromatography detection apparatus based on dielectric barrier discharge emission spectroscopy as claimed in claim 1, wherein said metal tube is a stainless steel tube, and said metal electrode is a copper wire.
9. The gas chromatography detection device based on dielectric barrier discharge emission spectroscopy as claimed in claim 1, wherein the quartz tube is 50mm long, 1.6mm in inner diameter and 3mm in outer diameter.
10. The gas chromatography detection apparatus based on dielectric barrier discharge emission spectroscopy as claimed in claim 1, wherein the dielectric barrier discharge gas is a carrier gas of a gas chromatograph, and the carrier gas pressure is 0.1 MPa.
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| CN202010039696.4A CN111044664A (en) | 2020-01-15 | 2020-01-15 | Gas chromatography detection device based on dielectric barrier discharge emission spectrum |
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| CN202010039696.4A CN111044664A (en) | 2020-01-15 | 2020-01-15 | Gas chromatography detection device based on dielectric barrier discharge emission spectrum |
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