CN114740099A - Method for analyzing sulfides and total sulfur in hydrogen by using enhanced plasma chromatography - Google Patents
Method for analyzing sulfides and total sulfur in hydrogen by using enhanced plasma chromatography Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 48
- 239000011593 sulfur Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 150000003568 thioethers Chemical class 0.000 title claims abstract 4
- 238000004587 chromatography analysis Methods 0.000 title abstract description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 20
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 20
- 238000004458 analytical method Methods 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 238000012360 testing method Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 54
- 239000012159 carrier gas Substances 0.000 claims description 28
- 239000001307 helium Substances 0.000 claims description 13
- 229910052734 helium Inorganic materials 0.000 claims description 13
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- 230000003321 amplification Effects 0.000 claims description 7
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- 239000012466 permeate Substances 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 12
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 10
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 10
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 10
- 150000004763 sulfides Chemical class 0.000 description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 210000005056 cell body Anatomy 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01N30/64—Electrical detectors
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of analysis and test, and particularly relates to an analysis method for sulfides and total sulfur in hydrogen. The invention adopts the enhanced plasma chromatography to directly sample (without sample concentration), quickly and accurately measure the content of the sulfur in the hydrogen in common form, and the lowest detection limit of the hydrogen sulfide can reach below 0.001 mu mol/mol (namely 1 ppb). The method adopts a sulfur converter to convert all form sulfur into hydrogen sulfide and sulfur dioxide components, and then uses an enhanced plasma chromatograph to detect, and obtains the total sulfur content according to the total amount of the converted hydrogen sulfide and sulfur dioxide components; the method has the advantages of accuracy, reliability, high detection efficiency, simplicity in operation, strong applicability and the like.
Description
Technical Field
The invention belongs to the technical field of analysis and test, and particularly relates to a method for analyzing sulfides and total sulfur in hydrogen by using enhanced plasma chromatography.
Background
Trace impurities in hydrogen gas seriously affect the performance of fuel cells, and in particular, sulfides are irreversibly adsorbed on the surface of electrodes and cause permanent degradation of the performance of fuel cells. The quality index requirements of the hydrogen for the fuel cell vehicle are successively established at home and abroad, and the national standard 'fuel hydrogen for proton exchange membrane fuel cell vehicles' (GB/T37244-2018) and the international standard ISO14687:2019(E) clearly require that the total sulfur in the hydrogen for the fuel cell vehicle is not more than 0.004 mu mol/mol (namely 4 ppbv). Therefore, trace amounts of sulfur and total sulfur in hydrogen for fuel cell vehicles are critical and difficult to detect accurately.
GB/T37244 teaches the total sulphur content to be carried out according to the method given in ASTM D7652, namely concentration desorption + Sulphur Chemiluminescence (SCD). The method can meet the requirement of detection limit, but has higher equipment price and more auxiliary equipment.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a method for analyzing sulfide and total sulfur in hydrogen by using enhanced plasma chromatography. The method adopts a sulfur converter, completely converts the form sulfur into hydrogen sulfide and sulfur dioxide components, and then uses an enhanced plasma chromatograph to detect, and obtains the total sulfur content according to the total amount of the converted hydrogen sulfide and sulfur dioxide components; the method has the advantages of accuracy, reliability, high detection efficiency, simplicity in operation, strong applicability and the like.
In order to achieve the above purposes, the invention adopts the technical scheme that:
a method for analyzing sulfide and total sulfur in hydrogen by using an enhanced plasma method comprises the following steps:
1) selecting a chromatographic column;
2) setting a condition of the enhanced plasma discharge detector;
3) switching on a power supply and a gas circuit, and opening a switch of the enhanced plasma discharge detector;
when the sulfur in hydrogen form is tested, sample introduction is carried out, sample gas is carried into a chromatographic column through carrier gas, sulfides in the sample gas are sequentially separated and flow out of the chromatographic column, and then the sample gas enters an enhanced plasma discharge detector for detection; the method comprises the following steps of performing discharge ionization by using sample gas and helium gas of a discharge cell, enabling characteristic wavelengths of ionized samples to pass through an optical filter, collecting sample electric signals through a photodiode and an amplification board, and sending photoelectric signals collected by a detector into a chromatographic workstation to calculate and analyze results;
or, when testing total sulfur in hydrogen, introducing the sample gas into a sulfur converter, after all sulfur in the sample gas is converted into hydrogen sulfide and sulfur dioxide components, detecting according to the test of sulfur in hydrogen, namely, the converted hydrogen sulfide and sulfur dioxide components are sent into a chromatographic column as the sample gas, the sulfide in the sample gas is sequentially separated and flows out of the chromatographic column, enters an enhanced plasma detector for detection, discharge ionization is carried out by utilizing the sample gas and helium in a discharge cell, the characteristic wavelength of the ionized sample is passed through an optical filter, sample electric signals are collected through a photodiode and an amplification plate, and photoelectric signals collected by the detector are sent into a chromatographic workstation for calculating and analyzing results.
Furthermore, the selected chromatographic column is Restek XL sulfurfur; 1mmx1mmx1m 1/16; and (5) micro-filling the column.
Further, the carrier gas is helium, and the carrier gas is purified by a purifier before use, wherein the temperature of the purifier is 350 ℃.
Further, the column conditions were: the initial temperature of the injection port is 30 deg.C, maintaining for 1.5min, the temperature gradient is 75 deg.C/min, the final chromatographic column temperature is 230 deg.C, maintaining for 2min, cooling to 30 deg.C, and maintaining for 3 min.
Furthermore, the enhanced plasma chromatograph adopts high-purity helium as carrier gas after two-stage purification, and adopts nitrogen as valve driving gas.
Further, the pre-column pressure of the enhanced plasma chromatograph is 21psi at a constant pressure, the initial column flow is 19mL/min, the permeation tube flow is 10mL/min, and the valve is purged for 5 mL/min.
Further, the enhanced plasma chromatograph should use high-purity helium after two-stage purification as carrier gas, fully purge the gas path system, and turn on the "power switch" and "chromatographic column temperature" of the instrument during the purge. Under the normal condition, after the temperature of the carrier gas purifier is stable and the complete set of gas circuit system is completely replaced, the 'switch' is started to start analysis. The whole analysis is injected at least twice in parallel, and if the relative deviation of two adjacent measurements is within 10%, the sample analysis is completed.
Furthermore, the temperature of a carrier gas purifier matched with the enhanced plasma chromatograph is 350 ℃, and the temperature of a chromatographic column is 30-230 ℃.
Further, the range of detection of sulfides and total sulfur in hydrogen is 0.001. mu. mol/mol to 1000. mu. mol/mol (V/V).
An enhanced plasma discharge detector (hereinafter abbreviated as EPD) is a detector based on dielectric barrier discharge plasma, a high-frequency and high-intensity electromagnetic field is applied around a cell body of the detector, a carrier gas is ionized into plasma (plasma) under the action of the high-frequency and high-intensity electromagnetic field, when a sample enters the cell body of the detector, the plasma is ionized and emits light with different wavelengths, an optical signal is converted into an electrical signal through a photodiode, and the intensity of the electrical signal is in direct proportion to the concentration of the sample. The EPD detector is more versatile than conventional selective detectors and more selective than conventional generic detectors because it responds to most molecules. The detector cell body is designed based on the dielectric barrier discharge principle. It includes a plasma controller with characteristics controlled by a single-chip microcomputer. In addition to having one set of electrodes to sustain the plasma discharge, this system has two additional electrodes. One group is used to stabilize and focus the plasma, which reduces the wall charge build-up on the surface, which is a problem with conventional dielectric barrier discharge technology. This is the main source of noise due to spatial motion. In addition, the stabilizing field helps to reduce the sputtering effect that occurs on the internal surface of the quartz cell over time. This is due to the bombardment of the surface by energetic electrons. Over time, the plasma cell wall surface under the discharge electrode becomes rough. This ultimately leads to increased peak broadening and reduced sensitivity. And the other group is used for injecting electrons, so that the ionization efficiency is improved. Increasing the seed electrons by the electron injection electrode may improve the overall ionization efficiency or so-called reaction rate. With these designs, the sensitivity of EPD can be improved by about 10 times over conventional plasma detectors.
Compared with the prior art, the invention has the positive effects that:
the method can directly sample (without sample concentration), and quickly and accurately measure the content of common sulfur and total sulfur in hydrogen.
(II) the lowest detection limit of hydrogen sulfide can reach below 0.001 mu mol/mol.
Drawings
FIG. 1 is a schematic diagram of an EPD detector;
the labels in the figure are: 1 is discharge cell, 2 is stable plasma, 3 is composite electrode, 4 is plasma beam, 5 is filter, 6 is photodiode, 7 is amplification plate, 8 is gas inlet, 9 is evacuation.
FIG. 2 is a schematic diagram of a process flow of a method for analyzing sulfides and total sulfur in hydrogen by using enhanced plasma chromatography:
the labels in the figure are: 1 is sample gas, 2 is carrier gas, 3 is carrier gas purifier, 4 is chromatographic column, 5 is permeator, 6 is EPD detector, 7 is data processing.
FIG. 3 is an analytical spectrum of example 1
FIG. 4 is an analytical spectrum of example 2
FIG. 5 is an analytical spectrum of example 3
FIG. 6 is an analytical spectrum of example 4
Detailed Description
The embodiments of the present invention are described below by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that, in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A device for analyzing sulfide and total sulfur in hydrogen by using enhanced plasma chromatography comprises a sample gas inlet 1, a carrier gas inlet 2, a carrier gas purifier 3, a chromatographic column 4, a permeator 5, an EPD detector 6 and a data processing device 7; the carrier gas inlet 2 is connected with the carrier purifier 3, so that the carrier is purified in the carrier purifier 3, the purity of purified carrier gas is more than or equal to 99.9999%, sample gas from the sample gas inlet 1 and the purified carrier gas enter the chromatographic column 4 together, sulfides in the sample gas are sequentially separated and flow out of the chromatographic column 4, the permeator 5 contains a certain content of doped gas, the improvement of the sensitivity of the detector is facilitated, the sample gas enters the EPD detector 6 for detection after passing through the permeator 5, and data obtained through detection is input into the data processing device 7 for data processing, so that the carrier gas is obtained.
The chromatographic columns used in the following examples are both Restek-XL sulfurr; 1mmx1mmx1m 1/16; and (5) micro-filling the column.
Example 1:
the morphological sulfur analysis in hydrogen is carried out by adopting the device for analyzing the sulfide and the total sulfur in the hydrogen by using the enhanced plasma chromatography, wherein in a standard gas (a sample gas): the hydrogen sulfide, carbonyl sulfide, methyl mercaptan, ethyl mercaptan, and dimethyl disulfide were each set to 80 ppb.
The method specifically comprises the following steps:
1) selecting a chromatographic column: Restek-XL sulfurur; 1mmx1mmx1m 1/16; micro-filling columns;
2) setting a condition of the enhanced plasma discharge detector;
3) when testing the sulfur in hydrogen, sample introduction is carried out, the sample gas is carried into a chromatographic column through carrier gas, and sulfides in the sample gas are sequentially separated and flow out of the chromatographic column and enter an enhanced plasma discharge detector for detection; the method comprises the steps of utilizing sample gas and helium gas of a discharge cell to carry out discharge ionization, enabling characteristic wavelengths of ionized samples to pass through an optical filter, collecting sample electric signals through a photodiode and an amplification board, and sending photoelectric signals collected by a detector into a chromatographic workstation to calculate and analyze results.
The temperature of the carrier gas purifier is 350 ℃; the initial temperature of the chromatographic column is 30 deg.C, maintaining for 5min, the temperature gradient is 50 deg.C/min, the final temperature of the chromatographic column is 150 deg.C, maintaining for 1min, cooling to 30 deg.C, and maintaining for 2 min.
The results are shown in FIG. 3, which shows an analytical spectrum in which hydrogen sulfide and carbonyl sulfide cannot be separated, and ethanethiol and dimethyldisulfide cannot be separated.
Example 2:
the morphological sulfur analysis in hydrogen was carried out using the same procedure as in example 1, except that:
the temperature of the carrier gas purifier is 350 ℃; the initial temperature of the chromatographic column is 30 ℃, the temperature is kept for 1.5min, the temperature gradient is 75 ℃/min, the final temperature of the chromatographic column is 230 ℃, the temperature is kept for 2min, and the temperature is cooled to 30 ℃ and kept for 3 min.
Standard gas (sample gas to be measured): the analytical spectra of hydrogen sulfide, carbonyl sulfide, methyl mercaptan, ethyl mercaptan and dimethyl disulfide are respectively 80ppb, and are shown in FIG. 4.
Example 3:
the same procedure as in example 1 was used for the analysis of morphological sulfur in hydrogen, except that:
the temperature of the carrier gas purifier is 350 ℃; initial temperature of chromatographic column is 30 deg.C, maintaining for 1.5min, temperature gradient is 75 deg.C/min, final temperature of chromatographic column is 230 deg.C, maintaining for 2min, cooling to 30 deg.C, and maintaining for 3 min.
Standard gas (sample gas to be measured): the analytical spectrum of the standard gas of 100ppb each of hydrogen sulfide, carbonyl sulfide, methyl mercaptan, ethyl mercaptan and dimethyl disulfide in hydrogen is shown in FIG. 5.
Example 4:
the analysis of the total sulfur in the hydrogen is carried out by adopting the device for analyzing the sulfide and the total sulfur in the hydrogen by using the enhanced plasma chromatography.
The method specifically comprises the following steps:
1) selecting a chromatographic column: Restek-XL sulfurur; 1mmx1mmx1m 1/16; micro-filling columns;
2) setting a condition of the enhanced plasma discharge detector;
3) when analyzing the total sulfur in hydrogen, sample introduction is carried out, after the sample gas is completely converted into hydrogen sulfide through a sulfur converter, the hydrogen sulfide is carried into a chromatographic column through carrier gas, and sulfides in the sample gas are sequentially separated and flow out of the chromatographic column and enter an enhanced plasma discharge detector for detection; the method comprises the steps of utilizing sample gas and helium gas of a discharge cell to carry out discharge ionization, enabling characteristic wavelengths of ionized samples to pass through an optical filter, collecting sample electric signals through a photodiode and an amplification board, and sending photoelectric signals collected by a detector into a chromatographic workstation to calculate and analyze results.
The temperature of the carrier gas purifier is 350 ℃; initial temperature of chromatographic column is 30 deg.C, maintaining for 1.5min, temperature gradient is 75 deg.C/min, final temperature of chromatographic column is 230 deg.C, maintaining for 2min, cooling to 30 deg.C, and maintaining for 3 min.
Standard gas (sample gas to be measured): hydrogen sulfide, carbonyl sulfide, methyl mercaptan, ethyl mercaptan, dimethyl disulfide each 1 ppm. The analysis of the spectrum is shown in FIG. 6.
| Serial number | Component name | Retention time (min) | Concentration (ppm) |
| 1 | Total sulfur (in terms of hydrogen sulfide) | 2.38 | 6 |
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The above-described embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (10)
1. A method for analyzing sulfide and total sulfur in hydrogen by using an enhanced plasma method is characterized by comprising the following steps:
1) selecting a chromatographic column;
2) setting a condition of the enhanced plasma discharge detector;
3) when testing the sulfur in hydrogen, sample introduction is carried out, the sample gas is carried into a chromatographic column through carrier gas, and sulfides in the sample gas are sequentially separated and flow out of the chromatographic column and enter an enhanced plasma discharge detector for detection; the method comprises the following steps of performing discharge ionization by using sample gas and helium gas of a discharge cell, enabling characteristic wavelengths of ionized samples to pass through an optical filter, collecting sample electric signals through a photodiode and an amplification board, and sending photoelectric signals collected by a detector into a chromatographic workstation to calculate and analyze results; when testing the total sulfur in hydrogen, introducing the sample gas into a sulfur converter, after all the sulfur in the sample gas is converted into hydrogen sulfide and sulfur dioxide components, detecting according to the test of sulfur in hydrogen, and finally obtaining an analysis result.
2. The method as claimed in claim 1, wherein, in the total sulfur in hydrogen test, the sample gas is introduced into a sulfur converter, after all the sulfur in the sample gas is converted into hydrogen sulfide and sulfur dioxide components, the hydrogen sulfide and sulfur dioxide components are detected according to the hydrogen sulfur test, namely, the converted hydrogen sulfide and sulfur dioxide components are sent into a chromatographic column as the sample gas, the sulfide in the sample gas is sequentially separated and flows out from the chromatographic column, the sample gas and helium are sent into an enhanced plasma detector for detection, the discharge ionization is carried out by using the sample gas and helium in a discharge cell, the characteristic wavelength of the ionized sample is passed through a light filter, the sample electric signal is collected through a photodiode and an amplification plate, and the photoelectric signal collected by the detector is sent into a chromatographic workstation for calculation and analysis.
3. The method of claim 1, wherein the selected column is Restek-XL Sulfur; 1mmx1mmx1m 1/16; and (5) micro-filling the column.
4. The method of claim 1 wherein the carrier gas is helium and the carrier gas is purified by a purifier prior to use, the purifier being at a temperature of 350 ℃.
5. The method of claim 1, wherein the column conditions are: the initial temperature of the injection port is 30 deg.C, maintaining for 1.5min, the temperature gradient is 75 deg.C/min, the final chromatographic column temperature is 230 deg.C, maintaining for 2min, cooling to 30 deg.C, and maintaining for 3 min.
6. The method of claim 1, wherein the enhanced plasma discharge detector uses high purity helium as a carrier gas after two-stage purification, and uses nitrogen as a valve driving gas.
7. The method of claim 1, wherein the enhanced plasma discharge detector is used before use, the gas circuit system is fully purged by using high-purity helium after two-stage purification as a carrier gas, and a power switch and a chromatographic column temperature of the instrument are turned on during purging; after the temperature of the carrier gas purifier is stable and the complete set of gas circuit system is fully replaced, starting a switch to start analysis.
8. The method of claim 7, wherein the entire analysis is performed at least twice in parallel, and the sample analysis is completed if the relative deviation between two adjacent measurements is within 10%.
9. The method of claim 1, wherein the conditions for enhancing the plasma discharge detector are: the pre-column pressure was 21psi constant, initial column flow 19mL/min, permeate tube flow 10mL/min, and valve purge 5 mL/min.
10. The method of any one of claims 1-9, wherein sulfides and total sulfur in hydrogen are detected in the range of 0.001 μmol/mol to 1000 μmol/mol (V/V).
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| US20030133836A1 (en) * | 2000-07-18 | 2003-07-17 | Siemens Ag | System for determining total sulfur content |
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