CN103884794A - Method for measuring trace hydrogen sulfide gas in atmosphere - Google Patents
Method for measuring trace hydrogen sulfide gas in atmosphere Download PDFInfo
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- CN103884794A CN103884794A CN201410123429.XA CN201410123429A CN103884794A CN 103884794 A CN103884794 A CN 103884794A CN 201410123429 A CN201410123429 A CN 201410123429A CN 103884794 A CN103884794 A CN 103884794A
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- shaped pipe
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- hydrogen sulfide
- sulfide gas
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Abstract
The invention provides a method for measuring trace hydrogen sulfide gas in atmosphere. The method comprises the following steps: loading an adsorbent into a U-shaped pipe, connecting the two ends of the U-shaped pipe with a six-way valve which is arranged on a gas chromatogram through three-way valves respectively, keeping the six-way valve is in a sample loading state, suspending the U-shaped pipe above a liquid nitrogen container for pre-cooling for 2-3 minutes, vacuumizing through the three-way valve at one end, and introducing an atmospheric sample through the three-way valve at the other end; stopping introduction of the atmospheric sample and vacuumizing after adsorption of the hydrogen sulfide gas through the adsorbent is finished, rotating the three-way valves to turn the U-shaped pipe into an enclosed state, and performing thermal desorption on the U-shaped pipe at the temperature of 130 DEG C for 4 minutes; rapidly rotating the three-way valves, switching the six-way valve to a sample loading state, introducing sulfur-containing gas into the chromatogram along with carrier gas, and detecting by using a flame photometric detector. The method has the advantages of high precision and recovery rate, low detection limit, and is easy and convenient to operate.
Description
Technical field
The invention belongs to dusty gas determination techniques field, relate in particular to a kind of method of measuring trace hydrogen sulfide gas in atmosphere.
Background technology
Sulfuretted hydrogen is the one of volatile sulfur compounds, from natural source and artificial source.Because chemical activity is strong, in atmosphere, easily there is photochemical oxidation reaction, be oxidized to SO
4 2-, to the certain contribution of being formed with of sulfate aerosol, sulfate aerosol affects the reflectivity of solar radiation and cloud, thereby weather is impacted.Sulfuretted hydrogen is also typical odorant simultaneously, and people's odor threshold all, below ppb level, except causing the impact in the sense of taste, can also directly be detrimental to health, and also can cause murder by poisoning to plant.Measuring as can be seen here micro-sulfuretted hydrogen is biogeochemical cycle, the needs of evaluation to atmosphere environment impact of understanding sulphur.But it is low that sulfuretted hydrogen has concentration in atmosphere, be generally ppb level, the features such as easily absorption, poor chemical stability, cannot directly measure, and are difficult for detecting accurately, and the foundation of its analytical approach is one of internationally recognized technical barrier.
Summary of the invention
The object of the present invention is to provide a kind of method of measuring trace hydrogen sulfide gas in atmosphere, be intended to solve sulfuretted hydrogen and in atmosphere, there is the features such as low, the easy absorption of concentration, poor chemical stability, and then cause directly measuring and be difficult for detecting problem accurately.
The present invention is achieved in that a kind of method of measuring trace hydrogen sulfide gas in atmosphere, comprises the following steps:
(1) adsorbent is encased in U-shaped pipe, U-shaped pipe two ends are connected with the six-way valve being arranged in gas chromatography by T-valve respectively, six-way valve is dress sample state, U-shaped pipe is suspended on to the top precooling 2～3 minutes of containing liquid nitrogen container, vacuumize by one end T-valve, other end T-valve enters atmospheric sample;
(2) adsorbent completes after hydrogen sulfide gas absorption, and stop into atmospheric sample and vacuumize, swivel tee valve, making U-shaped pipe is closed state, and U-shaped pipe is placed at 130 DEG C of temperature to thermal desorption 4 minutes;
(3) rapid swivel tee valve, open six-way valve is sample introduction state simultaneously, sulfurous gas enters chromatogram with carrier gas, is detected by flame photometric detector (FPD).
Preferably, in step (1), described adsorbent is 60～80 object Chromosorb G, and described Chromosorb G first soaks with acetone before use, then at 250 DEG C, is dried 10～20 hours.
Preferably, in step (1), described U-shaped pipe is polytetrafluoroethylmaterial material preparation; Described U-shaped bore is 4mm, long 8～12cm; In described U-shaped pipe, fill 200～300mg adsorbent.
Preferably, in step (1), described atmospheric sample is (18～20) ml.min by the speed of U-shaped pipe
-1.
Preferably, in step (1), described atmospheric sample is before passing through U-shaped pipe, first by CaCl is housed
2.2H
2the drying tube of O.
Preferably, in step (3), described GC conditions is: 50 DEG C of column temperatures, 100 DEG C of vaporizer temperature; Described flame photometric detector (FPD) working temperature is 220 DEG C; Described carrier gas is the high pure nitrogen of flow velocity 2.96ml/min; Air A flow velocity: 70ml/min, air B flow velocity: 185ml/min; Hydrogen flow rate: 210ml/min.
Compare and the shortcoming and defect of prior art, the present invention has following beneficial effect: precision of the present invention and the recovery are all better, and detectability is low, and simple, convenient.
Brief description of the drawings
Fig. 1 is cryosorption process flow diagram in the embodiment of the present invention;
Fig. 2 is thermal desorption gas analysis process flow diagram in the embodiment of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment
1 instrument and reagent
1.1 main experimental provision and analytical instrument
GC-7890II type gas chromatograph (GC～FPD joins six-way valve 3) (Shanghai Techcomp Instrument Ltd.), temperature control furnace (development voluntarily), minipump, U-shaped pipe 1, GS-GasPro quartz capillary column: long 30m, aperture 0.53mm.
1.2 main agents
H
2s calibrating gas, 1000ppm (purchased from Beijing Hai Pubeifen gas industry company limited)
2 chromatographic conditions
Column temperature: 50 DEG C; Vaporizer temperature: 100 DEG C; FPD detecting device, temperature: 220 DEG C; Carrier gas is high pure nitrogen, flow velocity: 2.96ml/min; Air A flow velocity: 70ml/min, air B flow velocity: 185ml/min; Hydrogen flow rate: 210ml/min.
Gas chromatography detecting device used is flame photometric detector (FPD), and principle of work is exactly that the flame that utilizes hydrogen and air burning to produce makes detected material ionization, then detects.Both hydrogen was burning gas, and entered nozzle after nitrogen premixed, and in the time that nitrogen flow rate is fixing, along with the increase of hydrogen flow rate, output signal also increases thereupon, and declines rapidly after reaching a maximal value.
Air is combustion-supporting gas, provides O for generating CHO+
2, the H that still burning generates simultaneously
2o and CO
2clean gas the morning.The size of flow is to determine according to the difference of instrument instructions and detection gas.
3 test methods
The preparation of 3.1U type pipe 1
Homemade U-shaped pipe 1 is U-shaped polyfluortetraethylene pipe, and internal diameter is 4mm, is about 10cm.Before use, with acetone cleaning, dry.Interior filling Chromosorb G (60～80 order), approximately 200～300mg.Chromsorb G first soaks with acetone before use, then dry more than 10 hours at 250 DEG C.
The condensation adsorption of 3.2 samples
As shown in Figure 1, the two ends of the U-shaped pipe 1 of teflon are connected with the six-way valve 3 being arranged in gas chromatography by T-valve 2 respectively, are suspended on the top of containing liquid nitrogen container 4.When condensation adsorption, six-way valve 3 is dress sample state.First by U-shaped pipe 1 precooling 2～3 minutes, then by 1L sample under vacuum pump 5 acts on about 20ml.min
-1speed by U-shaped pipe 1, hydrogen sulfide containing gas, under the double action of low temperature and adsorbent, is retained in U-shaped pipe 1, remaining gas is discharged by minipump 5.In order to prevent that steam is at low temperatures in U-shaped pipe 1 inner accumulated, before passing through U-shaped pipe 1, first by CaCl is housed
2.2H
2the drying tube 6 of O.In order to prevent the absorption of hydrogen sulfide gas, pipeline is polyfluortetraethylene pipe, and the part that cannot replace with teflon, uses 0.02mol.L
-1phosphoric acid-acetone carry out pre-service, to reduce the absorption to sulfuretted hydrogen.
The desorb of 3.3 samples and test
As shown in Figure 2, after condensation, remove immediately liquid nitrogen, swivel tee valve 2, making U-shaped pipe 1 is closed state, prevents that sample runs off in the time of thermal desorption, U-shaped pipe 1 is put into heating furnace 7 desorbs, determine that by many groups of tests desorption temperature is 130 DEG C, the parsing time is 4 minutes, after 4 minutes, swivel tee valve 2 rapidly, open six-way valve 3 for sample introduction state, sulfurous gas enters chromatogram (not shown) with carrier gas, is detected by flame photometric detector (FPD) (not shown) simultaneously.After approximately 1 minute, rapidly six-way valve 3 is threaded to dress sample state, removes well heater, prepare sample introduction next time.
4 results and analysis
4.1 typical curve
4.1.1 the configuration of calibrating gas
In the large syringe of 100ml, inject high pure nitrogen, accurately measure a certain amount of hydrogen sulfide standard gas with micro syringe and inject wherein, after treating that gas reaches balance, constant volume, obtain the calibrating gas of certain mass concentration, be more successively diluted to desired concn with high pure nitrogen.
4.1.2 the drafting of typical curve
In the large syringe of 100ml, press calibrating gas configuration step, 1.41,2.82,4.23,5.64,7.05,14.1ug/L the mass concentration of typical curve of configuration is:, accurately get 0.1ml calibrating gas with micro syringe, press the step of 1.3.1 and 1.3.2, blow into concentration tube by nitrogen, then carry out stratographic analysis, each gas concentration is done three repetitions.Because flame photometric detector (FPD) is nonlinear to the response of sulphur, can not, with peak area quantification, therefore do linear regression with the logarithm of peak height h and the logarithm of mass concentration, regression equation is: lgh=3.077+1.996lgx, related coefficient: R=0.9958.Under identical test condition, enter the standard specimen of different volumes with syringe, standard specimen concentration is 14.1ug/L, the curve plotting on log-log plot by peak height and sample size, the range of linearity of curve is roughly between 0.15～7ng.
The precision of 4.2 methods and the recovery
By standard air distributing method, get certain density sulfuretted hydrogen sample gas Chromatographic Determination after cryosorption, thermal desorption, separately get certain density calibrating gas direct injected, the precision of two kinds of methods, as shown in table 1 below:
The precision (n=6) of table 1 method
In blank sample, add the sulfuretted hydrogen of two kinds of different qualities, gas Chromatographic Determination after cryosorption, thermal desorption, the recovery recording, as shown in table 2 below:
The blank recovery of standard addition (n=6) of table 2 method
From table 1 and table 2, within the requirement that the coefficient of variation of direct injected and low temperature concentrated sample introduction is all analyzed in ppb level, the recovery, between 88.5～90.25%, can meet and analyze requirement.
The detectability of 4.3 methods
The minimum detectability (MDL) of method is measured according to the method for Keith suggestion, the Standard Gases of parallel analysis 0.282ng～2.82ng 4 times, and the standard deviation of calculating measurement result, is multiplied by t-statistical value by standard deviation, is the detection limit of component.The detection limit that test records sulfuretted hydrogen is 0.192ng, if sample volume is 1L, the minimal detectable concentration of sulfuretted hydrogen is: 0.192ng/L.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. measure a method for trace hydrogen sulfide gas in atmosphere, it is characterized in that comprising the following steps:
(1) adsorbent is encased in U-shaped pipe, U-shaped pipe two ends are connected with the six-way valve being arranged in gas chromatography by T-valve respectively, six-way valve is dress sample state, U-shaped pipe is suspended on to the top precooling 2～3 minutes of containing liquid nitrogen container, vacuumize by one end T-valve, other end T-valve enters atmospheric sample;
(2) adsorbent completes after hydrogen sulfide gas absorption, and stop into atmospheric sample and vacuumize, swivel tee valve, making U-shaped pipe is closed state, and U-shaped pipe is placed at 130 DEG C of temperature to thermal desorption 4 minutes;
(3) rapid swivel tee valve, open six-way valve is sample introduction state simultaneously, sulfurous gas enters chromatogram with carrier gas, is detected by flame photometric detector (FPD).
2. the method for trace hydrogen sulfide gas in mensuration atmosphere as claimed in claim 1, it is characterized in that, in step (1), described adsorbent is 60～80 object Chromosorb G, described Chromosorb G first soaks with acetone before use, then at 250 DEG C, is dried 10～20 hours.
3. the method for trace hydrogen sulfide gas in mensuration atmosphere as claimed in claim 2, is characterized in that, in step (1), described U-shaped pipe is polytetrafluoroethylmaterial material preparation; Described U-shaped bore is 4mm, long 8～12cm; In described U-shaped pipe, fill 200～300mg adsorbent.
4. the method for trace hydrogen sulfide gas in mensuration atmosphere as claimed in claim 3, is characterized in that, in step (1), described atmospheric sample is (18～20) ml.min by the speed of U-shaped pipe
-1.
5. the method for trace hydrogen sulfide gas in mensuration atmosphere as claimed in claim 4, is characterized in that, in step (1), described atmospheric sample is before passing through U-shaped pipe, first by CaCl is housed
2.2H
2the drying tube of O.
6. the method for trace hydrogen sulfide gas in mensuration atmosphere as claimed in claim 5, is characterized in that, in step (3), described GC conditions is: 50 DEG C of column temperatures, 100 DEG C of vaporizer temperature; Described flame photometric detector (FPD) working temperature is 220 DEG C; Described carrier gas is the high pure nitrogen of flow velocity 2.96ml/min; Air A flow velocity: 70ml/min, air B flow velocity: 185ml/min; Hydrogen flow rate: 210ml/min.
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Cited By (4)
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|---|---|---|---|---|
| CN104181228A (en) * | 2014-09-18 | 2014-12-03 | 电子科技大学 | Gas circuit device capable of accelerating response of trace gas integrated detector |
| CN108982722A (en) * | 2018-09-25 | 2018-12-11 | 佛山科学技术学院 | A kind of alternating temperature gas pre-concentration sample injection method and device |
| CN110095556A (en) * | 2019-05-21 | 2019-08-06 | 中国测试技术研究院化学研究所 | Measure the thermal desorption-gas chromatograph and detection method of sulfide content in hydrogen |
| CN110161139A (en) * | 2019-05-23 | 2019-08-23 | 中国辐射防护研究院 | A kind of large volume non-quantitative sample injection method using gas chromatograph separation Kr-85 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104181228A (en) * | 2014-09-18 | 2014-12-03 | 电子科技大学 | Gas circuit device capable of accelerating response of trace gas integrated detector |
| CN104181228B (en) * | 2014-09-18 | 2017-02-22 | 电子科技大学 | Method capable of accelerating response of trace gas integrated detector |
| CN108982722A (en) * | 2018-09-25 | 2018-12-11 | 佛山科学技术学院 | A kind of alternating temperature gas pre-concentration sample injection method and device |
| CN110095556A (en) * | 2019-05-21 | 2019-08-06 | 中国测试技术研究院化学研究所 | Measure the thermal desorption-gas chromatograph and detection method of sulfide content in hydrogen |
| CN110161139A (en) * | 2019-05-23 | 2019-08-23 | 中国辐射防护研究院 | A kind of large volume non-quantitative sample injection method using gas chromatograph separation Kr-85 |
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Application publication date: 20140625 |