CN112557122A - Sampling device for measuring trace sulfide in hydrogen - Google Patents
Sampling device for measuring trace sulfide in hydrogen Download PDFInfo
- Publication number
- CN112557122A CN112557122A CN202011431892.2A CN202011431892A CN112557122A CN 112557122 A CN112557122 A CN 112557122A CN 202011431892 A CN202011431892 A CN 202011431892A CN 112557122 A CN112557122 A CN 112557122A
- Authority
- CN
- China
- Prior art keywords
- gas
- pipe
- enrichment
- liquid nitrogen
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2226—Sampling from a closed space, e.g. food package, head space
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2226—Sampling from a closed space, e.g. food package, head space
- G01N2001/2238—Sampling from a closed space, e.g. food package, head space the gas being compressed or pressurized
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
- G01N2030/126—Preparation by evaporation evaporating sample
Abstract
The invention discloses a sampling device for measuring trace sulfide in hydrogen, which comprises a gas guide pipe, wherein the gas guide pipe is sequentially communicated with a needle valve, a gas flowmeter and a concentration and enrichment pipe, one end of the concentration and enrichment pipe is provided with an enrichment pipe connector, the other end of the concentration and enrichment pipe is provided with a gas chromatography connector, the concentration and enrichment pipe is arranged inside a cold hydrazine liquid nitrogen tank, the top of the cold hydrazine liquid nitrogen tank is provided with a liquid nitrogen tank cover plate, a liquid nitrogen charging hole is formed in the liquid nitrogen tank cover plate, the enrichment pipe connector and the gas chromatography connector are arranged above the liquid nitrogen tank cover plate, and the enrichment pipe connector is provided with an electric heating wire connector. Under the action of low temperature, sulfide in a certain volume of hydrogen is solidified and concentrated in a concentration and enrichment pipe filled with an adsorbent, chromatographic carrier gas is introduced into the concentration and enrichment pipe and the concentration and enrichment pipe is heated, the solidified and concentrated sulfide is evaporated and separated out, and enters a gas chromatograph along with the carrier gas to further detect the content of the sulfide.
Description
Technical Field
The invention relates to the technical field of chemical production sampling, in particular to a sampling device for measuring trace sulfides in hydrogen.
Background
In some chemical processes, the requirement on the content of sulfides in hydrogen is high, the content of the sulfides is required to be controlled at ppb level, the sample introduction amount of gas chromatography is limited by volume, the detection limit of the chromatography cannot meet the detection requirement on ppb level trace sulfides in the hydrogen, and the sulfides are easily adsorbed by using sampling articles such as air bag bladders and the like.
Disclosure of Invention
The invention aims to provide a sampling device for measuring trace sulfides in hydrogen, and solves the problems that the existing sampling articles are easy to adsorb sulfides and cannot meet the detection requirements.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to a sampling device for measuring trace sulfide in hydrogen, which comprises a gas guide pipe, wherein the gas guide pipe is sequentially communicated with a needle valve, a gas flowmeter and a concentration and enrichment pipe, one end of the concentration and enrichment pipe is provided with an enrichment pipe connector, the other end of the concentration and enrichment pipe is provided with a gas chromatography connector, the concentration and enrichment pipe is arranged inside a cold hydrazine liquid nitrogen tank, the top of the cold hydrazine liquid nitrogen tank is provided with a liquid nitrogen tank cover plate, a liquid nitrogen filling hole is formed in the liquid nitrogen tank cover plate, the enrichment pipe connector and the gas chromatography connector are arranged above the liquid nitrogen tank cover plate, and an electric heating wire connector is arranged on the enrichment pipe connector.
Furthermore, the concentration and enrichment pipe comprises a wavy hollow glass pipe, an electric heating wire is arranged on the outer side of the glass pipe, heat insulation cotton is arranged on the outer side of the electric heating wire, and fillers in the enrichment pipe are filled in the glass pipe.
Still further, a temperature control sensor is arranged inside the electric heating wire, and 25% beta' -dicyanoethyl ether is adopted as a filler in the enrichment tube.
Still further, the gas conduit is provided as a transparent polytetrafluoroethylene hose.
Still further, the gas chromatography connector is set as a stainless steel needle.
Still further, the enriching tube connector is made of stainless steel.
A sampling mode for measuring trace sulfide in hydrogen is characterized in that: the sampling mode adopts the sampling device for measuring the trace sulfide in the hydrogen to realize the sampling of the trace sulfide in the hydrogen, and the specific process steps are as follows:
the first step is as follows: before sampling, the gas guide pipe is communicated with the needle valve, the gas flowmeter and the concentration and enrichment pipe in sequence;
the second step is that: during sampling, the gas conduit is communicated with a hydrogen sampling point;
the third step: opening a hydrogen valve, and allowing the gas to be detected to sequentially flow into the needle valve, the gas flowmeter and the concentration enrichment pipe through the gas guide pipe;
the fourth step: adjusting the needle valve, and controlling the gas flow rate to be 0.2L/min;
the fifth step: after the gas flow rate is stable, placing the concentration and enrichment pipe in the cold hydrazine liquid nitrogen tank, and covering a cover plate of the liquid nitrogen tank;
and a sixth step: stopping sampling when the sampling volume reaches 2L, closing a hydrogen valve, disconnecting the enriching tube connector and the gas guide pipe, immediately plugging the gas chromatography connector by using a silica gel pad, and disconnecting all connection points of the gas guide pipe;
the seventh step: when detecting sample sulphide, follow concentrated enrichment pipe take out in the cold hydrazine liquid nitrogen tank, and will the gas chromatography connector with enrichment pipe connector is connected to gas chromatography on, then will electric heating wire connects the switch on, lets in the carrier gas, starts the heating function, the concentrated sulphide of solidification in the concentrated enrichment pipe is gone out through heating evaporation, gets into gas chromatograph along with the carrier gas and detects.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention relates to a sampling device for measuring trace sulfide in hydrogen, which comprises a gas guide pipe, a needle valve, a gas flowmeter, a concentration pipe connector, a gas chromatography connector, a cold trap liquid nitrogen tank, a liquid nitrogen tank cover plate, an electric heating wire connector, heat preservation cotton, an electric heating wire and a filler in the concentration pipe, wherein the needle valve is used for controlling the flow rate of gas entering the sampling device; the gas flow meter is used for monitoring the flow velocity and flow of gas entering the sampling device; the cold hydrazine liquid nitrogen tank is used for cooling hydrogen, prolonging the retention time of the gas in the enrichment tube and ensuring that sulfides in the gas are adsorbed; the concentration enrichment tube is made of glass materials, so that the sulfide in hydrogen is prevented from being adsorbed, and 25% beta-dicyanoethyl ether is adopted as a filler in the enrichment tube, so that the sulfide in the hydrogen is completely adsorbed; the gas chromatography connector is a stainless steel needle head, can be conveniently connected to a chromatograph, and has good adaptability with the instrument; according to the invention, sulfides in the hydrogen are enriched and concentrated, the detection requirement that the detection limit of a gas chromatograph cannot meet the content of trace ppb-level sulfur in the hydrogen is solved, the problem that gas sampling articles such as an air bag and a bladder adsorb sulfur is avoided due to the glass material of the enrichment tube, and the detection repeatability is good after the sampling device is used.
Drawings
The invention is further illustrated in the following description with reference to the drawings.
FIG. 1 is a schematic view of a sampling structure according to the present invention;
FIG. 2 is a schematic structural diagram of a sulfide detection sample according to the present invention;
FIG. 3 is a cross-sectional view of a concentrating enrichment tube of the present invention;
description of reference numerals: 1. a gas conduit; 2. a needle valve; 3. a gas flow meter; 4. filling a liquid nitrogen hole; 5. a gas chromatography connector; 6. a cover plate of the liquid nitrogen tank; 7. a concentration enrichment pipe; 8. a cold hydrazine liquid nitrogen tank; 9. a enriching pipe connector; 10. an electrical heater wire connector; 7-1, heat preservation cotton; 7-2, an electric heating wire; 7-3, enriching the filler in the tube; 7-4, glass tube.
Detailed Description
As shown in fig. 1-3, a sampling device for measuring trace sulfides in hydrogen comprises a gas conduit 1, wherein the gas conduit 1 is sequentially communicated with a needle valve 2, a gas flowmeter 3 and a concentration and enrichment pipe 7, an enrichment pipe connector 9 is installed at one end of the concentration and enrichment pipe 7, a gas chromatography connector 5 is installed at the other end of the concentration and enrichment pipe 7, the concentration and enrichment pipe 7 is arranged inside a cold hydrazine liquid nitrogen tank 8, a liquid nitrogen tank cover plate 6 is arranged at the top of the cold hydrazine liquid nitrogen tank 8, a liquid nitrogen filling hole 4 is formed in the liquid nitrogen tank cover plate 6, the enrichment pipe connector 9 and the gas chromatography connector 5 are arranged above the liquid nitrogen tank cover plate 6, and an electric heating wire connector 10 is arranged on the enrichment pipe connector 9; the needle valve 2 is used for controlling the flow rate of gas entering the sampling device; the gas flowmeter 3 is used for monitoring the flow velocity and flow of gas entering the sampling device; the cold hydrazine liquid nitrogen tank 8 is used for cooling hydrogen, prolonging the retention time of the gas in the concentration and enrichment pipe 7 and ensuring that sulfide in the gas is completely adsorbed.
Specifically, as shown in fig. 3, the concentration and enrichment pipe 7 comprises a wavy hollow glass pipe 7-4, the glass material is adopted to avoid adsorption on sulfides in hydrogen, an electric heating wire 7-2 is arranged on the outer side of the glass pipe 7-4, heat insulation cotton 7-1 is arranged on the outer side of the electric heating wire 7-2, and filling materials 7-3 in the concentration pipe are filled in the glass pipe 7-4.
A temperature control sensor is arranged in the electric heating wire 7-2, and 25% beta' -dicyanoethyl ether is adopted as the filler 7-3 in the enrichment tube, so that the sulfide in the hydrogen is completely adsorbed.
The gas conduit 1 is provided as a transparent polytetrafluoroethylene hose.
The gas chromatography connector 5 is a stainless steel needle head, can be conveniently connected to a chromatograph, and has good adaptability to the instrument.
The enriching pipe connector 9 is made of stainless steel.
A sampling mode for measuring trace sulfide in hydrogen is characterized in that: the sampling mode adopts the sampling device for measuring the trace sulfide in the hydrogen to realize the sampling of the trace sulfide in the hydrogen, and the specific process steps are as follows:
the first step is as follows: before sampling, the gas conduit 1 is communicated with the needle valve 2, the gas flowmeter 3 and the concentration enrichment pipe 7 in sequence;
the second step is that: during sampling, the gas conduit 1 is communicated with a hydrogen sampling point;
the third step: opening a hydrogen valve, and allowing the gas to be detected to sequentially flow into the needle valve 2, the gas flowmeter 3 and the concentration and enrichment pipe 7 through the gas guide pipe 1;
the fourth step: adjusting the needle valve 2, and controlling the gas flow rate to be 0.2L/min;
the fifth step: after the gas flow rate is stable, placing the concentration and enrichment pipe 7 in the cold hydrazine liquid nitrogen tank 8, and covering the liquid nitrogen tank cover plate 6;
and a sixth step: stopping sampling when the sampling volume reaches 2L, closing a hydrogen valve, disconnecting the enrichment pipe connector 9 and the gas guide pipe 1, immediately plugging the gas chromatography connector 5 by a silica gel pad, preventing air from being sucked back into the sampling device, and disconnecting all connection points of the gas guide pipe 1;
the seventh step: when detecting sample sulphide, the concentrated enrichment pipe 7 is taken out of the cold trap liquid nitrogen tank 8, the gas chromatography connector 5 and the enrichment pipe connector 9 are connected to the gas chromatography, then the electric heating wire connector 10 is powered on, carrier gas is introduced, the heating function is started, and the sulphide solidified and concentrated in the concentrated enrichment pipe 7 is evaporated by heating and enters a gas chromatograph along with the carrier gas for detection.
Under the action of low temperature, sulfide in a certain volume of hydrogen is solidified and concentrated in a concentration enrichment pipe filled with an adsorbent, chromatographic carrier gas is introduced into the concentration enrichment pipe and the concentration enrichment pipe is heated, the solidified and concentrated sulfide is evaporated and separated out and enters a gas chromatograph along with the carrier gas so as to detect the content of the sulfide; the invention solves the problem that the detection limit of a gas chromatograph cannot meet the detection requirement of the trace ppb level sulfur content in hydrogen, the glass material of the concentration enrichment tube avoids the problem that gas sampling articles such as an air bag, a bladder and the like adsorb sulfur, and the detection repeatability is good after the sampling device is used.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A sampling device for measuring trace sulfide in hydrogen is characterized in that: including gas conduit (1), gas conduit (1) communicates needle valve (2), gas flowmeter (3) and concentrated enrichment pipe (7) in proper order, the one end of concentrated enrichment pipe (7) is provided with enrichment union coupling head (9), the other end of concentrated enrichment pipe (7) is provided with gas chromatography connector (5), concentrated enrichment pipe (7) set up the inside at cold hydrazine liquid nitrogen container (8), the top of cold hydrazine liquid nitrogen container (8) is provided with liquid nitrogen tank cover board (6), be provided with on liquid nitrogen tank cover board (6) and fill liquid nitrogen hole (4), enrichment union coupling head (9) with gas chromatography connector (5) set up the top of liquid nitrogen container cover board (6), be provided with electric heating line joint (10) on enrichment union coupling head (9).
2. The sampling device for measuring trace sulfides in hydrogen according to claim 1, wherein: the concentration and enrichment pipe (7) comprises a wave-shaped hollow glass pipe (7-4), an electric heating wire (7-2) is arranged on the outer side of the glass pipe (7-4), heat insulation cotton (7-1) is arranged on the outer side of the electric heating wire (7-2), and an enrichment pipe inner filler (7-3) is filled in the glass pipe (7-4).
3. The sampling device for measuring trace sulfides in hydrogen according to claim 2, wherein: a temperature control sensor is arranged in the electric heating wire (7-2), and 25% beta' -dicyanoethyl ether is adopted as the filler (7-3) in the enrichment tube.
4. The sampling device for measuring trace sulfides in hydrogen according to claim 1, wherein: the gas conduit (1) is arranged as a transparent polytetrafluoroethylene hose.
5. The sampling device for measuring trace sulfides in hydrogen according to claim 1, wherein: the gas chromatography connector (5) is a stainless steel needle.
6. The sampling device for measuring trace sulfides in hydrogen according to claim 1, wherein: the enriching pipe connector (9) is made of stainless steel.
7. A sampling mode for measuring trace sulfide in hydrogen is characterized in that: the sampling mode adopts the sampling device for measuring the trace sulfide in the hydrogen as claimed in any one of claims 1 to 6 to realize the sampling of the trace sulfide in the hydrogen, and the specific process steps are as follows:
the first step is as follows: before sampling, the gas guide pipe (1) is communicated with the needle valve (2), the gas flowmeter (3) and the concentration enrichment pipe (7) in sequence;
the second step is that: during sampling, the gas conduit (1) is communicated with a hydrogen sampling point;
the third step: opening a hydrogen valve, and allowing the gas to be detected to sequentially flow into the needle valve (2), the gas flowmeter (3) and the concentration enrichment pipe (7) through the gas guide pipe (1);
the fourth step: adjusting the needle valve (2) and controlling the gas flow rate to be 0.2L/min;
the fifth step: after the gas flow rate is stable, placing the concentration and enrichment pipe (7) in the cold hydrazine liquid nitrogen tank (8), and covering the liquid nitrogen tank cover plate (6);
and a sixth step: stopping sampling when the sampling volume reaches 2L, closing a hydrogen valve, disconnecting the enrichment pipe connector (9) and the gas guide pipe (1), immediately plugging the gas chromatography connector (5) by a silica gel pad, and disconnecting all connection points of the gas guide pipe (1);
the seventh step: when detecting sample sulphide, follow concentrated enrichment pipe (7) take out in cold hydrazine liquid nitrogen tank (8), and will gas chromatography connector (5) with enrichment pipe connector (9) are connected to gas chromatography, then will electrical heating wire connector (10) switch on, let in the carrier gas, start heating function, concentrated sulphide of concentrated enrichment pipe (7) internal cure is through heating evaporation come out, gets into gas chromatograph along with the carrier gas and detects.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011431892.2A CN112557122A (en) | 2020-12-07 | 2020-12-07 | Sampling device for measuring trace sulfide in hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011431892.2A CN112557122A (en) | 2020-12-07 | 2020-12-07 | Sampling device for measuring trace sulfide in hydrogen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112557122A true CN112557122A (en) | 2021-03-26 |
Family
ID=75060005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011431892.2A Pending CN112557122A (en) | 2020-12-07 | 2020-12-07 | Sampling device for measuring trace sulfide in hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112557122A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114324691A (en) * | 2021-12-30 | 2022-04-12 | 江苏省环境监测中心 | Method for improving sulfide detection precision |
-
2020
- 2020-12-07 CN CN202011431892.2A patent/CN112557122A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114324691A (en) * | 2021-12-30 | 2022-04-12 | 江苏省环境监测中心 | Method for improving sulfide detection precision |
| CN114324691B (en) * | 2021-12-30 | 2023-08-04 | 江苏省环境监测中心 | Method for improving sulfide detection precision |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN213397846U (en) | Sampling device for measuring trace sulfide in hydrogen | |
| CN112557122A (en) | Sampling device for measuring trace sulfide in hydrogen | |
| CN102650623A (en) | Device for detection of low-concentration Freon in seawater and production method thereof | |
| CN103018378A (en) | Gas chromatograph with oil-gas separation function and gas chromatography process for determination of trace moisture in insulating oil | |
| CN206609695U (en) | Portable head space purges enriching apparatus | |
| CN103792310B (en) | For the sampling device that water body release gas gas phase measures | |
| CN203365398U (en) | In-situ headspace sample injector | |
| CN208239396U (en) | Pressure swing adsorption separation CH4/N2Performance evaluation device for adsorbent for mixed gas | |
| CN103344728A (en) | In-situ headspace sample injector | |
| CN203719978U (en) | Standard gas preparation device | |
| CN108760959B (en) | Pressure-reducing gas-liquid balancing device with automatic pressure-controlling and sample-measuring functions | |
| CN100425978C (en) | Device for determining halium in metal using pulse heat conduction method and its application | |
| CN112798723B (en) | Quantitative analysis device for detecting gas chromatograph blowback gas | |
| CN201397320Y (en) | Experimental device for desorbing H2S and CO2 in alcohol amine solution | |
| CN216718313U (en) | Focusing concentration-gas chromatography sulfide detection system | |
| Smith et al. | Some useful techniques and accessories for adaptation of the gas chromatograph to soil nitrogen studies | |
| CN219475116U (en) | Sample injection device and system for testing moisture content of battery conductive paste | |
| CN207036543U (en) | Online air pre-concentration device | |
| CN209166919U (en) | Flash vaporized sample introduction sampler | |
| CN207571088U (en) | A kind of needle type extraction device for concentrating volatile benzene homologues | |
| CN203720155U (en) | Sample feeding device for measuring gas phase of water body release gas | |
| CN115856178B (en) | Headspace solid-phase microextraction sampling device and method | |
| CN2620277Y (en) | Gas flow circuit device for heat desorption apparatus | |
| CN108693283A (en) | The automatic sampling pretreatment unit and method of hydrogen phosphide are measured for gas chromatography | |
| CN111720734B (en) | Sampling system on liquid hydrogen storage tank |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |