CN107478742A - A kind of chromatographic analysis systems and its method of wide-range measure sulfide in gas - Google Patents
A kind of chromatographic analysis systems and its method of wide-range measure sulfide in gas Download PDFInfo
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- CN107478742A CN107478742A CN201710673619.2A CN201710673619A CN107478742A CN 107478742 A CN107478742 A CN 107478742A CN 201710673619 A CN201710673619 A CN 201710673619A CN 107478742 A CN107478742 A CN 107478742A
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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
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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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
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
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Abstract
The invention discloses the chromatographic analysis systems and its method that a kind of wide-range using single-column, bivalve, dual detector determines sulfide in gas, by using gas circuit cutting technique and pipeline, valve coated inner wall technology, combined using FPD detectors with thermal conductivity detector (TCD), can realize that quick, accurate, wide-range tests and analyzes to the various sulfide in current various industrial gasses, fuel gas and light industry and food industry gas.
Description
Technical field
The invention belongs to analysis and testing technology field, and in particular to a kind of gas phase color of wide-range measure sulfide in gas
Compose analysis system and its method.
Background technology
Natural gas and other fuel gas are all clean energy resourcies, at home using increasingly extensive.But these fuel gas
In contain sulfide, sulfide not only pollutes environment, harm health, can also corrode feed-line.Due to these fuel gas
Using area constantly expands, and consumption figure increases year by year, has reached 2058 billion cubic meters to 2016, the sulfide meeting for release of burning
Large effect is caused to environment.For the consideration of environmental protection, country is to sulfide in natural gas and other fuel gas
Content's index is increasingly strict, for example, newly revise《Natural gas》National standard proposes more to the sulfide content in natural gas
Strict requirements.
In addition, in petrochemical industry, chemical process, the presence of sulfide can cause the poisoning of not sulfur resistant catalyst, make it
Activity decrease, or even lose activity completely, cause heavy losses to industrial production.
In the various gas products that the light industries such as food use, it is also desirable to monitor sulfide content.
Due to differences such as the place of production, purposes, species, the changes of contents of sulfide in gas are larger.In particular with various new
The appearance of type fuel gas, the measurement to the sulfide in fuel gas have spread over coal gas, oven gas, coal bed gas, life
The fields such as material air-liquid gas, natural gas used for automobile.Sulphur compound in natural gas mainly includes：Hydrogen sulfide, sulphur carbonoxide, sulphur
Alcohol, thioether and disulphide etc..The natural gas of different sources, its sulphidic species and content differ, and well head natural gas contains
There is variform sulphur, the content of hydrogen sulfide may be up to 10%.The combustion gas such as coal gas, coal bed gas, biogas, its sulfide group
There is larger difference with conventional gas into content.The content of sulfide is usually less than 0.1ppm (V/V) in coal gas；Coke oven
Also variform sulphur is contained in coal gas, the content of hydrogen sulfide generally arrives thousands of ppm (1 × 10 hundreds of-6)；Sulphur in biogas
Change hydrogen content generally in tens ppm between percentage composition.
At present, both at home and abroad high content sulfide analysis in gas are used with chemical analysis method, chemical analysis operation more
Cumbersome, time-consuming longer, the degree of accuracy is not high.Analysis to low content sulfide more using sulfur chemiluminescent detector (SCD) method and
Flame photometric detector (FPD) method.SCD main advantages compared with other methods are the equimolar response and height to sulfide
Sensitivity, therefore use sulfur chemiluminescent gas chromatography can easily realize the measure of Sulfur and total sulfur in gas.But
Be SCD gas chromatographies for most of users, there is stricter use condition, and instrument price is higher, can not
Large area industrial application.
Traditional FPD gas chromatographs are mostly single detector flow.It can be only done 0.1ppm to 200ppm or so in sample
Sulfide analysis, the sulfide composition of excessive concentrations causes the damage of detector sometimes in gas.Moreover, in natural gas
The species of sulfide is more, complicated.Some macromolecular sulfide, such as disulphide, retention time is very long in the chromatography column, reaches
40~more than 50min, not only analysis time grow, and due to retention time grow, appearance evening, peak shape is flat, content it is low often by
Noise takeover, the accuracy of impact analysis result.
The sulfide that traditional FPD, PFPD (pulsive flame photometric detector) detector detects in various gases is a kind of
Preferable state, especially suitable for the simple gas analysis sample of comparison of ingredients.FPD, PFPD detector have to form sulfide
There is good Monitoring lower-cut, but upper limit of detection only up to reach 2%, and this is for some H2Well head of the S contents 5%~10%
Natural gas can not quick detection.
Some sulfide properties are active, particularly hydrogen sulfide, and easily absorption is on pipeline inner wall, or the vulcanization adsorbed on tube wall
Thing is desorbed, and the accuracy of impact analysis result, therefore, this is also the problem that chromatography analysis sulfide must solve.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of denier of quick and precisely analyzing in multiple gases to normal
Measure the wide-range sulfide analysis gas chromatography system and its method of sulfide, the system can ppb (1 × 10 in detection gas-9) level denier sulfide, and can detection H2S is up to 10% gas, for domestic enterprise provide it is a kind of it is more convenient, fast,
Accurate analysis method for gases.
The chromatographic analysis systems of the wide-range measure sulfide in gas of the present invention, including：With the He of the first six-way valve 3
The sample introduction part that quantity tube 1 is formed；With the first six-way valve 3, quantity tube 1, GasPro capillary columns 5, the second six-way valve 6 and flame light
Spend the first analysis part that detector 13 is formed；With with the first six-way valve 3, quantity tube 1, GasPro capillary columns 5, the second six-way valve
6 and thermal conductivity detector (TCD) 7 form the second analysis part.
Above-mentioned first analysis part is used to analyze cos, concentration of hydrogen sulfide≤100ppm gas；Above-mentioned second analysis
Part is used to analyze cos, concentration of hydrogen sulfide >=100ppm gas.
The above-mentioned six-way valve 6 of first six-way valve 3 and second can be manually or automatically to switch six-way valve.
In above-mentioned chromatographic analysis systems, the leading portions of GasPro capillary columns 5 installs the part flow arrangement of shunting/not additional, with suitable
Answer change in concentration of the different sulfide in analysis is used.
In above-mentioned chromatographic analysis systems, in addition to injection port, outlet, needle valve, pressure-reducing valve, pressure maintaining valve, gas
Conventional components and the materials such as road pipeline, carrier gas bottle, auxiliary carrier gas bottle, carrier gas, these can be commercially by commercially available.
In order to avoid corrosion of the sulfide to analysis system pipeline, valve inwall, the present invention further enters to these parts
Row preservative treatment：Pipeline, valve inwall material selection stainless steel, such as 316 stainless steels；Utilize overlay cut-off sulfide and pipe
The contact in road, valve inwall, sulfide is avoided to be chemically reacted with pipeline, valve inwall；Coating material selects hydrogenated butyronitrile
Vulcanization of rubber glue or modified phenol phenol aldehyde type epoxy resin, it is good with pipeline, the attachment of valve inwall, it is evenly distributed, to hydrogenate fourth
Nitrile rubber cured properties is preferable；Coated technique uses normal temperature coated technique, i.e., cold painting technique；Its advantage is that normal temperature processing is not broken
Bad pipeline connects and valve seal material；Coating method is to be well mixed coating material with auxiliary agent, by disperseing grinding technics
Compo is made, is injected using inwall and rolls tubing, make coating levelling uniform；Then 24h is air-dried at 20 DEG C, after 1 week
It is fully cured.
The method analyzed with above-mentioned chromatographic analysis systems sulfide in multiple gases, comprises the following steps：
(1) sample introduction：Sample gas is entered in quantity tube 1 by six-way valve 3, replaces the gas (reference chart in quantity tube 1
1)；
(2) A is analyzed：Switch the first six-way valve 3, the sample gas in quantity tube 1 is sent into GasPro capillary columns 5, sample by carrier gas
Cos, hydrogen sulfide, methyl mercaptan in product, ethyl mercaptan, thiophene, dimethyl disulfide, methyl sulfide, ethyl sulfide, thiophane, two sulphur
Change carbon sulfides to separate and flow out successively in GasPro capillary columns 5, detected (with reference to figure 2) into flame photometric detector 13；
(3) B is analyzed：When cos, concentration of hydrogen sulfide are more than 100ppm, the sample gas in quantity tube 1 is sent into by carrier gas
GasPro capillary columns 5, cos, hydrogen sulfide in sample, methyl mercaptan, ethyl mercaptan, thiophene, dimethyl disulfide, methyl sulfide, second sulphur
Ether, thiophane, carbon disulfide sulfides are separated and flowed out successively in GasPro capillary columns 5, and now program control device treats carbonyl
When sulphur, 2 S component leading peak will flow out GasPro capillary columns 5, switch the second six-way valve 6, by cos, 2 S component
Thermal conductivity detector (TCD) 7 is imported to analyze；After treating cos, 2 S component outflow, program control device switches the second six-way valve again
6, remaining sulfide composition in GasPro capillary columns 5 is switched back into flame photometric detector 13 and detected (with reference to figure 3).
According to some specific embodiments of the present invention, after cos and hydrogen sulfide outflow Gaspro capillary columns, use
Temperature programming, 10 DEG C of heating rate~15 DEG C/min, 180 DEG C of final temperature.Gaspro capillary columns flow rate of carrier gas be 1.5~
2.5ml/min.Thermal conductivity detector (TCD) operating temperature is 160 DEG C~180 DEG C, and flame photometric detector operating temperature is 220 DEG C~260
℃。
The analyze data obtained to flame photometric detector (FPD) and thermal conductivity detector (TCD) (TCD), is handled using chromatographic data
Passage folding, it is incorporated on same baseline, and using a kind of sulfide of bearing calibration analysis various concentrations.It is more logical
Road industrial data integrate merging be a kind of known technology, referred to as " passage mergings ", its technical principle Anhai Doan with
What AlonHalevy was collaborateed《Data integration principle》Discuss.
Technique according to the invention scheme, when the cos containing more than 100ppm, hydrogen sulfide in sample gas, pass through
Switch the second six-way valve cut from Gaspro chromatographic columns isolate be sent into thermal conductivity detector (TCD) and obtain signal response, depending on
Measure analyze data.But hydrogen sulfide is a kind of high corrosion component, and corrosion is also easy to produce to metal material, influences detector performance.
Therefore, analyze high content hydrogen sulfide gas sample, propose higher requirement to thermal conductivity detector (TCD) performance, the present invention further from
Following aspect sets about handling thermal conductivity detector (TCD), to overcome the problem：
1) heated filament treatment technology is studied, ensures heated filament corrosion resistance, good reproduction is still kept after continuous sample introduction --- choosing
Make heated filament with platinum tungsten filament, intensity is big, and resistivity is high, high sensitivity, and resistance to oxidation is corrosion-resistant.
2) conductance cell uses micro-volume pond, can improve sensitivity as much as possible, ensures that peak type more sharply narrows, more important
, micro- pond body product can realize that detector docks with capillary column, be easy to component in GasPro capillary columns to enter detector.
3) passivation treatment technology is used to conductance cell, the element that sample gas is contacted in thermal conductivity detector (TCD) is used
Sulfinert coatings, one layer of fine and close metal film coatings are formed, reduce absorption and the residual of hydrogen sulfide, extend Thermal Conductivity
Device service life, good sensitivity is kept for a long time, it is ensured that reach decay resistance and good analysis reappearance.
Sulfinert coating is Restek companies of U.S. famous mark brand resistant to sulfur coating products.
It is of the invention compared with the various analysis methods of sulfide in previous detection gas, pass through traditional flame photometric detection
Device is combined with improved thermal conductivity detector (TCD), using advanced gas circuit cutting technique, and is aided with the blunt of pipeline, valve and conductance cell
Change handling process, realize quick, the Accurate Determining of wide scope sulfide content in gas.
The present invention has the advantages of instrument cost is low, analyst coverage is wide, and operating efficiency is high.With a set of chromatograph, once enter
Sample, the measure of content sulfide within can completing in gaseous sample from ppm to 10.Monitoring lower-cut：0.05×10-6(V/
V), upper limit of detection：10% (V/V, in terms of hydrogen sulfide), detection time：Within 15min.
Brief description of the drawings
Fig. 1 is analysis system sample introduction view of the present invention；
Fig. 2 is that analysis system of the present invention analyzes view to low concentration sample；
Fig. 3 is that analysis system of the present invention analyzes view to enriched sample；
1-quantity tube, the import of 2-sample gas, 3-sample introduction six-way valve, 4-shunting/not part flow arrangement, 5-Gaspro capillarys
Tubing string, 6-automatic switchover six-way valve, 7-thermal conductivity detector (TCD), 8-pressure maintaining valve, 9-steel cylinder pressure-reducing valve, 10-air steel cylinder,
11-combustion-supporting gas cylinder, 12-needle valve, 13-flame photometric detector, the threeway of 14-gas circuit, the outlet of 15-sample gas, 16-carry
Gas cylinder；
Fig. 4 is the well head natural gas sulfur-bearing composition chromatography figure of embodiment 1；
Fig. 5 is the coke-stove gas sulfur-bearing composition chromatography figure of embodiment 2；
Fig. 6 is the biogas sulfur-bearing composition chromatography figure of embodiment 3.
Embodiment
Used chromatographic analysis systems in the following examples, including：With the first six-way valve 3 and the structure of quantity tube 1
Into sample introduction part；With the first six-way valve 3, quantity tube 1, GasPro capillary columns 5, the second six-way valve 6 and flame photometric detector
13 the first analysis parts formed；With with the first six-way valve 3, quantity tube 1, GasPro capillary columns 5, the second six-way valve 6 and thermal conductivity
The second analysis part that detector 7 is formed.Above-mentioned first analysis part is used to analyze cos, concentration of hydrogen sulfide≤100ppm
Gas；Above-mentioned second analysis part is used to analyze cos, concentration of hydrogen sulfide >=100ppm gas.
To the sulfide of various concentrations, it is detected and analyzed using different analysis parts, so as to real with set of system
The detection of existing wide-range, is applicable a variety of sulfurous gas.
The above-mentioned six-way valve 6 of first six-way valve 3 and second can be manually or automatically to switch six-way valve, and automatic valve to detect
Analysis is more succinct convenient.In above-mentioned chromatographic analysis systems, the leading portions of GasPro capillary columns 5 installs shunting/do not shunt dress additional
Put, to adapt to change in concentration of the different sulfide in analysis is used.
In above-mentioned chromatographic analysis systems, in addition to injection port, outlet, needle valve, pressure-reducing valve, pressure maintaining valve, gas
Conventional components and the materials such as road pipeline, carrier gas bottle, auxiliary carrier gas bottle, carrier gas, its mounting means and link position, art technology
Personnel can know after present disclosure is read, or obtain one way in which with reference to description of the invention accompanying drawing.
In order to avoid corrosion of the sulfide to analysis system pipeline, valve inwall, the present invention further enters to these parts
Row preservative treatment：Pipeline, the stainless steel of valve inwall material selection 316；With the cold painting technique of hydrogenized nitrile-butadiene rubber vulcanized rubber to pipe
Road and valve are coated.
In order to improve performance of the thermal conductivity detector (TCD) in corrosive environment, the present invention makees the heat of thermal conductivity detector (TCD) from platinum tungsten filament
Silk, conductance cell use micro-volume pond, and the element to contacting sample gas in thermal conductivity detector (TCD) uses Sulfinert coatings, carries out
Passivation Treatment.
The method analyzed with above-mentioned chromatographic analysis systems sulfide in multiple gases, comprises the following steps：
(1) sample introduction：Sample gas is entered in quantity tube 1 by six-way valve 3, replaces the gas (reference chart in quantity tube 1
1)；
(2) A is analyzed：Switch the first six-way valve 3, the sample gas in quantity tube 1 is sent into GasPro capillary columns 5, sample by carrier gas
Cos, hydrogen sulfide, methyl mercaptan in product, ethyl mercaptan, thiophene, dimethyl disulfide, methyl sulfide, ethyl sulfide, thiophane, two sulphur
Change carbon sulfides to separate and flow out successively in GasPro capillary columns 5, detected (with reference to figure 2) into flame photometric detector 13；
(3) B is analyzed：When cos, concentration of hydrogen sulfide are more than 100ppm, the sample gas in quantity tube 1 is sent into by carrier gas
GasPro capillary columns 5, cos, hydrogen sulfide in sample, methyl mercaptan, ethyl mercaptan, thiophene, dimethyl disulfide, methyl sulfide, second sulphur
Ether, thiophane, carbon disulfide sulfides are separated and flowed out successively in GasPro capillary columns 5, and now program control device treats carbonyl
When sulphur, 2 S component leading peak will flow out GasPro capillary columns 5, switch the second six-way valve 6, by cos, 2 S component
Thermal conductivity detector (TCD) 7 is imported to analyze；After treating cos, 2 S component outflow, program control device switches the second six-way valve again
6, remaining sulfide composition in GasPro capillary columns 5 is switched back into flame photometric detector 13 and detected (with reference to figure 3).
Explained below by way of specific embodiment is further to the content of the invention of the present invention, but should not be construed as the present invention
Scope be only limitted to following example, can will be each in following instance according to the invention thinking and entire contents of the present invention
Technical characteristic makes appropriate combination/replacement/adjustment/modification etc., and this is will be obvious to those skilled in the art that still
Belong to the category that the present invention protects.
The chromatographic condition of analysis system see the table below：
Embodiment 1
Sample：Well head natural gas；
Method and chromatographic analysis system：See foregoing.
Analysis result：It is shown in Table 1.
Analyze chromatogram：See Fig. 4.
The well head natural gas sulfur-bearing composition analysis result of table 1
Embodiment 2
Sample：Coke-stove gas；
Method and chromatographic analysis system：See foregoing.
Analysis result：It is shown in Table 2.
Analyze chromatogram：See Fig. 5.
The coke-stove gas sulfur-bearing composition analysis result of table 2
| Ingredient names | Retention time [min] | Content (mg/m3) |
| Hydrogen sulfide | 2.375 | 8798.0 |
| Cos | 3.595 | 24.6 |
| Carbon disulfide | 8.772 | 69.6 |
| Ethyl mercaptan | 12.077 | 71.1 |
| Thiophene | 12.923 | 153.4 |
| Methyl sulfide | 13.111 | 155.6 |
| Total sulfur | / | 9277.6 |
Embodiment 3
Sample：Biogas；
Method and chromatographic analysis system：See foregoing.
Analysis result：It is shown in Table 3.
Analyze chromatogram：See Fig. 6.
The biogas sulfur-bearing composition analysis result of table 3
| Ingredient names | Retention time [min] | Content (mg/m3) |
| Hydrogen sulfide | 1.775 | 678.9 |
| Cos | 2.957 | 88.1 |
| Carbon disulfide | 6.387 | 52.9 |
| Ethyl mercaptan | 11.123 | 31.2 |
| Thiophene | 12.487 | 35.6 |
| Total sulfur | / | 890.2 |
The analysis system of the present invention has the advantages of instrument cost is low, analyst coverage is wide, and operating efficiency is high, analysis is rapid.
With a set of chromatograph, single injected sampling, the measure of content sulfide within can completing in gaseous sample from ppm to 10.Inspection
Survey lower limit：0.05 × 10-6 (V/V), upper limit of detection：10% (V/V, in terms of hydrogen sulfide), detection time：Within 15min.
Claims (10)
- A kind of 1. chromatographic analysis systems of wide-range measure sulfide in gas, it is characterised in that including：It is logical with the one or six The sample introduction part that valve and quantity tube are formed；With the first six-way valve, quantity tube, GasPro capillary columns, the second six-way valve and flame light Spend the first analysis part that detector is formed；With with the first six-way valve, quantity tube, GasPro capillary columns, the second six-way valve and heat Lead the second analysis part of detector composition.
- 2. the chromatographic analysis systems of wide-range measure sulfide in gas according to claim 1, it is characterised in that First analysis part is used to analyze cos-containing, concentration of hydrogen sulfide≤100ppm gas；Second analysis part is used In analysis cos-containing, concentration of hydrogen sulfide >=100ppm gas.
- 3. the chromatographic analysis systems of wide-range measure sulfide in gas according to claim 1, it is characterised in that First six-way valve and the second six-way valve are manually or automatically to switch six-way valve.
- 4. the chromatographic analysis systems of wide-range measure sulfide in gas according to claim 1, it is characterised in that Shunting/not part flow arrangement is installed additional in the leading portion of GasPro capillary columns.
- 5. the chromatographic analysis systems of wide-range measure sulfide in gas according to claim 1, it is characterised in that Pipeline, the valve inwall material selection stainless steel of the analysis system；And with cold painting technique by hydrogenized nitrile-butadiene rubber vulcanized rubber or Modified phenol phenol aldehyde type epoxy resin is well mixed with auxiliary agent, and compo is made by scattered grinding technics, is coated uniformly on Pipeline, valve inwall.
- 6. the chromatographic analysis systems of wide-range measure sulfide in gas according to claim 1, it is characterised in that The heated filament of the thermal conductivity detector (TCD) makees heated filament from platinum tungsten filament；Conductance cell uses micro-volume pond；And use Sulfinert coatings pair Conductance cell does Passivation Treatment.
- A kind of 7. chromatographic analysis systems of the measure of the wide-range described in claim 1~6 any one sulfide in gas The method analyzed sulfide in gas, comprises the following steps：(1) sample introduction：Sample gas is entered in quantity tube by the first six-way valve, replaces the gas in quantity tube；(2) A is analyzed：Switch the first six-way valve, the sample gas in quantity tube is sent into GasPro capillary columns by carrier gas, the sulphur in sample Compound is separated and flowed out successively in GasPro capillary columns, is detected into flame photometric detector；(3) B is analyzed：When cos, concentration of hydrogen sulfide are more than 100ppm, the sample gas in quantity tube is sent into GasPro by carrier gas Capillary column, the sulfide in sample are separated and flowed out successively in GasPro capillary column, and now program control device treats cos, hydrogen sulfide When component leading peak will flow out GasPro capillary columns, switch the second six-way valve, cos, 2 S component are imported into Thermal Conductivity Device is analyzed；After treating cos, 2 S component outflow, program control device switches the second six-way valve again, by GasPro capillarys Remaining sulfide composition in post switches back into flame photometric detector detection.
- 8. the method according to claim 7 analyzed sulfide in gas, it is characterised in that in cos and sulphur After changing hydrogen component outflow Gaspro capillary columns, using temperature programming, 10 DEG C of heating rate~15 DEG C/min, final temperature 180 ℃。
- 9. the method according to claim 7 analyzed sulfide in gas, it is characterised in that Gaspro capillaries Post flow rate of carrier gas is 1.5~2.5ml/min.
- 10. the method according to claim 7 analyzed sulfide in gas, it is characterised in that thermal conductivity detector (TCD) Operating temperature is 160 DEG C~180 DEG C, and flame photometric detector operating temperature is 220 DEG C~260 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108732277A (en) * | 2018-07-31 | 2018-11-02 | 瑞丽中检检验认证有限公司 | The detection device and its detection method of total sulfur and sulfide in a kind of natural gas |
| CN111077258A (en) * | 2018-10-22 | 2020-04-28 | 中国石油天然气股份有限公司 | Sulfide analysis method |
| CN113341066A (en) * | 2021-05-24 | 2021-09-03 | 西南石油大学 | Multi-sensor fusion technology-based on-line detection method and system for tetrahydrothiophene concentration |
| WO2022242669A1 (en) * | 2021-05-18 | 2022-11-24 | 中国石油天然气股份有限公司 | Method and system for flame photometric online detection of sulfur-containing compound content in natural gas |
| CN117288916A (en) * | 2023-11-24 | 2023-12-26 | 四川兆雪科技有限公司 | High-precision detection device and method for online detection of natural gas odorizing agent concentration |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101126749A (en) * | 2007-09-26 | 2008-02-20 | 大庆石油管理局 | Quantitative analysis method for all form sulfur component of light carbon and its fractional distillation product |
| CN101799458A (en) * | 2010-03-25 | 2010-08-11 | 广东电网公司电力科学研究院 | Method for analyzing decomposition products of SF6 in electrical device |
| CN102297916A (en) * | 2011-05-21 | 2011-12-28 | 太原理工大学 | Chromatograph apparatus for detecting sulfides in gas material, and detection method thereof |
| US20140071435A1 (en) * | 2010-05-12 | 2014-03-13 | Intermolecular, Inc. | High Throughput Quantum Efficiency Combinatorial Characterization Tool and Method for Combinatorial Solar Test Substrates |
| JP2014228512A (en) * | 2013-05-27 | 2014-12-08 | 理研計器株式会社 | Portable gas detector |
-
2017
- 2017-08-09 CN CN201710673619.2A patent/CN107478742A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101126749A (en) * | 2007-09-26 | 2008-02-20 | 大庆石油管理局 | Quantitative analysis method for all form sulfur component of light carbon and its fractional distillation product |
| CN101799458A (en) * | 2010-03-25 | 2010-08-11 | 广东电网公司电力科学研究院 | Method for analyzing decomposition products of SF6 in electrical device |
| US20140071435A1 (en) * | 2010-05-12 | 2014-03-13 | Intermolecular, Inc. | High Throughput Quantum Efficiency Combinatorial Characterization Tool and Method for Combinatorial Solar Test Substrates |
| CN102297916A (en) * | 2011-05-21 | 2011-12-28 | 太原理工大学 | Chromatograph apparatus for detecting sulfides in gas material, and detection method thereof |
| JP2014228512A (en) * | 2013-05-27 | 2014-12-08 | 理研計器株式会社 | Portable gas detector |
Non-Patent Citations (2)
| Title |
|---|
| 司瑞刚 等: "利用气相色谱仪和硫化学发光检测器测定焦炉气制LNG工艺气中痕量硫化物", 《石油与天然气化工》 * |
| 常州磐诺仪器有限公司: "《常州磐诺仪器有限公司网站》", 22 March 2017 * |
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| CN108732277A (en) * | 2018-07-31 | 2018-11-02 | 瑞丽中检检验认证有限公司 | The detection device and its detection method of total sulfur and sulfide in a kind of natural gas |
| CN111077258A (en) * | 2018-10-22 | 2020-04-28 | 中国石油天然气股份有限公司 | Sulfide analysis method |
| WO2022242669A1 (en) * | 2021-05-18 | 2022-11-24 | 中国石油天然气股份有限公司 | Method and system for flame photometric online detection of sulfur-containing compound content in natural gas |
| GB2622511A (en) * | 2021-05-18 | 2024-03-20 | Petrochina Co Ltd | Method and system for flame photometric online detection of sulfur-containing compound content in natural gas |
| CN113341066A (en) * | 2021-05-24 | 2021-09-03 | 西南石油大学 | Multi-sensor fusion technology-based on-line detection method and system for tetrahydrothiophene concentration |
| CN113341066B (en) * | 2021-05-24 | 2022-04-08 | 西南石油大学 | Multi-sensor fusion technology-based on-line detection method and system for tetrahydrothiophene concentration |
| CN117288916A (en) * | 2023-11-24 | 2023-12-26 | 四川兆雪科技有限公司 | High-precision detection device and method for online detection of natural gas odorizing agent concentration |
| CN117288916B (en) * | 2023-11-24 | 2024-01-26 | 四川兆雪科技有限公司 | High-precision detection device and method for online detection of natural gas odorizing agent concentration |
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Application publication date: 20171215 |