CN109212047A - Sulfur-containing compound content analyzer in a kind of appropriate hydrocarbon gas - Google Patents
Sulfur-containing compound content analyzer in a kind of appropriate hydrocarbon gas Download PDFInfo
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- CN109212047A CN109212047A CN201710542340.0A CN201710542340A CN109212047A CN 109212047 A CN109212047 A CN 109212047A CN 201710542340 A CN201710542340 A CN 201710542340A CN 109212047 A CN109212047 A CN 109212047A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 79
- 239000011593 sulfur Substances 0.000 title claims abstract description 79
- 150000001875 compounds Chemical class 0.000 title claims abstract description 70
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 42
- 238000001514 detection method Methods 0.000 claims abstract description 36
- 238000004458 analytical method Methods 0.000 claims abstract description 27
- 238000013016 damping Methods 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005070 sampling Methods 0.000 claims description 32
- 239000012159 carrier gas Substances 0.000 claims description 23
- 239000005864 Sulphur Substances 0.000 claims description 19
- 150000003464 sulfur compounds Chemical class 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 18
- -1 Sulphur compound Chemical class 0.000 claims description 4
- 230000009849 deactivation Effects 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000005526 G1 to G0 transition Effects 0.000 claims description 2
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 35
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 28
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 17
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 17
- 238000000034 method Methods 0.000 description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000003915 liquefied petroleum gas Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- YWHLKYXPLRWGSE-UHFFFAOYSA-N Dimethyl trisulfide Chemical compound CSSSC YWHLKYXPLRWGSE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XLTBPTGNNLIKRW-UHFFFAOYSA-N methyldisulfanylethane Chemical compound CCSSC XLTBPTGNNLIKRW-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
-
- 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
- G01N30/60—Construction of the column
- G01N30/6004—Construction of the column end pieces
-
- 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
- G01N30/60—Construction of the column
- G01N30/6034—Construction of the column joining multiple columns
- G01N30/6039—Construction of the column joining multiple columns in series
-
- 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
-
- 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
- G01N30/60—Construction of the column
- G01N30/6004—Construction of the column end pieces
- G01N2030/6008—Construction of the column end pieces capillary restrictors
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
本发明涉及一种烃气体中含硫化合物含量分析仪，包括相互串联的第一样品定量环和第二样品定量环，所述第一样品定量环与微量含硫化合物检测单元相连，所述微量含硫化合物检测单元包括依次串联的第一分流进样口、含硫化合物分析柱、限流柱和硫选择性检测器；所述第二样品定量环与高浓度含硫化合物检测单元相连，所述高浓度含硫化合物检测单元包括第二分流进样口、非极性毛细管色谱柱、流路切换单元、阻尼柱、热导检测器、极性毛细管色谱柱和氢火焰离子化检测器。采用本发明所述的分析仪可以实现通过一次进样完成气中含宽浓度范围含硫化合物的定性结果，并据此得到各种含硫化合物的含量。
The invention relates to an analyzer for the content of sulfur-containing compounds in hydrocarbon gas, comprising a first sample quantitative loop and a second sample quantitative loop connected in series, the first sample quantitative loop is connected with a trace sulfur-containing compound detection unit, The trace sulfur-containing compound detection unit includes a first split injection port, a sulfur-containing compound analysis column, a limiting column and a sulfur-selective detector connected in series; the second sample quantitative loop is connected to the high-concentration sulfur-containing compound detection unit The high-concentration sulfur-containing compound detection unit includes a second split injection port, a non-polar capillary chromatographic column, a flow path switching unit, a damping column, a thermal conductivity detector, a polar capillary chromatographic column and a hydrogen flame ionization detector . Using the analyzer of the present invention can realize the qualitative results of sulfur-containing compounds in a wide concentration range in the gas through one sample injection, and obtain the content of various sulfur-containing compounds accordingly.
Description
Technical field
The present invention relates to a kind of gas chromatographicanalyzers, and in particular to sulfur-containing compound content analysis in a kind of appropriate hydrocarbon gas
Instrument.
Background technique
Sulfur-containing compound (hereinafter referred to as sulfide) is usually to make catalyst poisoning and inactivation in its deep-processing process in gas
Arch-criminal, controling and monitoring for sulfur content is content that various technical process are extremely paid close attention to.After its height not only seriously affects
The quality of continuous product, and have larger harm to pipeline and storage container.Current each refinery is by the liquefied petroleum gas of production
When (liquefied petroleum gas, LPG) is used as domestic fuel, according to GB11174-2011 " liquefied petroleum gas specification "
Regulation, it is desirable that total sulfur content is less than 343 × 10-6(volume fraction)；When as polymer grade ethylene or propylene industrial chemicals, sulphur contains
Amount (volume fraction) need to be controlled 1 × 10-6Below.In addition to this, constantly improve with environmental regulation, people are to oil product
Quality and its during production and application the control of discharge standard it is increasingly stringent, after gasoline has entered the state V epoch, to conduct
Sulfur content in the MTBE of gasoline additive also drops to 10mg/kg from the 50mg/kg in state IV epoch.This series of product control
Index processed is directed to the monitoring of sulfide in refinery gas, therefore, on the one hand from the angle that safe and environment-friendly, pipeline and equipment corrode
Degree sets out, and continuously improving desulfurization technology is the project that each refinery is faced, and on the other hand, the improvement of desulfurization technology is again largely
The upper progress dependent on to sulfide analysis method, this just illustrates the analysis method for carrying out sulfide in deep all kinds of gas
It studies increasingly important.
Currently, sulphur compound type analysis mostly uses gas-chromatography/sulphur selective detector joint technology in gas.Such skill
Art is widely used in that micro in gaseous sample (one pack system sulfide content is less than 100 × 10-6(volume fraction)) oxide morphology inspection
It surveys.
Therefore, when sample higher and wider sulfur compound distribution there are total sulfur content under test gas sample, such as
The process gas such as catalytic cracking process gas, coking process, the above method can carry out qualitative analysis, but can only be to wherein micro Containing Sulfur
It closes object and carries out quantitative analysis, 100 × 10 are greater than for one pack system sulfur content-6(volume fraction) component is needed using configuration flame
The chromatograph of ionization detector (FID) or thermal conductivity detector (TCD) (TCD) is detected, this is resulted in when vulcanization is closed in a sample
Object content range is from 10-9When tens~percent, two instruments, the analysis of sample introduction completion twice are at least needed.
In conclusion can not to complete this concentration range on a chromatograph wider for existing analytical equipment and method
Gaseous sample in the type analysis of sulfur-containing compound need at least two colors if a sample qualitative and quantitative analysis need to be carried out
Spectrometer, twice sample introduction.
Summary of the invention
The object of the present invention is to provide sulfur-containing compound content analyzer in a kind of appropriate hydrocarbon gas, the analyzer only need once into
The qualitative and quantitative analysis of volatile sulfur compound in gas can be completed in sample.
The present invention provides sulfur-containing compound content analyzer in a kind of appropriate hydrocarbon gas, the first sample including being serially connected is fixed
Ring and the second sample amounts ring are measured, the first sample amounts ring is connected with micro sulfur-containing compound detection unit, described micro
Sulfur-containing compound detection unit includes the first split sampling mouth being sequentially connected in series, analysis of sulfur compounds column, current limliting column and sulphur choosing
Selecting property detector；The second sample amounts ring is connected with high-concentration sulfur-containing compound test unit, the high-concentration sulfur-containing
Closing analyte detection unit includes the second split sampling mouth, nonpolar capillary chromatographic column, flow path switch unit, damping column, thermal conductivity inspection
Survey device, polarity capillary chromatographic column and flame ionization ditector, the second split sampling mouth and the nonpolar capillary
The connection of pipe chromatographic column, the nonpolarity capillary chromatographic column are connected with the hub-interface of the flow path switch unit, flow path switching
The interface of unit one end is sequentially connected with the damping column and the thermal conductivity detector (TCD), the interface of the other end and the polarity capillary
Pipe chromatographic column and the flame ionization ditector are sequentially connected.
In analyzer of the present invention, gaseous sample to be analyzed is collected by concatenated two sample amounts rings,
It is divided into two-way again, can be used for that all sulfur-containing compounds in sample are qualitative and micro sulfur-containing compound quantitative analysis all the way,
A piece analytical column of middle connection and current limliting column, can divide any traces of carbonyl sulfide and sulfur dioxide by sulphur selective detector
Analysis, another way enable it enter different chromatographic columns to different sample middle and high concentration sulfur-containing compound by flow path switch unit
Sulfur-containing compound is separated, and high-concentration sulfur-containing compound is made to separate and be detected one by one, can finally be completed by single injected sampling
The separation and detection of various sulfur-containing compounds in gas.
Analyzer sulfur-containing compound content range detected of the present invention is wider, both various micro- in detectable gas
The content for measuring sulfur-containing compound, goes back the higher hydrogen sulfide of detectable gas concentration, methyl mercaptan and ethyl mercaptan.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the structural schematic diagram containing wide concentration range sulfur-containing compound composition analyzer in gas of the present invention；
Fig. 2-4 is sulfur-containing compound chromatogram measured by the embodiment of the present invention 1.
Description of symbols
The two or six direction changeover valve of 1 the one or six direction changeover valve 2
3 fluidic switch, 4 analysis of sulfur compounds column
5 current limliting column, 6 damping column
78 polarity capillary chromatographic columns of nonpolar capillary chromatographic column
9 first split sampling mouth, 10 second split sampling mouth
11 sulphur selective detector, 12 thermal conductivity detector (TCD)
13 flame ionization ditector, 14 first sample amounts ring
15 second sample amounts ring, 16 sample introduction pipeline
17 first carrier gas line, 20 blow-down pipe
21 second carrier gas line, 18,19,22,24 pipeline
23 microplate flow path heartcut system, 25 hub-interface
26 first interface, 27 second interface
The interface of 111,112,113,114,115,116 the 1st direction changeover valves
The interface of 221,222,223,224,225,226 the 2nd 6 direction changeover valves
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Instrument detection of the present invention is divided into micro sulfur-containing compound detection unit and high-concentration sulfur-containing compound test unit,
In, the one pack system sulfide detection range of micro sulfur-containing compound detection unit is 20 × 10-9~100 × 10-6(volume point
Number), the one pack system sulfide detection range 0.01%~10% (volume fraction) of high-concentration sulfur-containing compound test unit.
As shown in Figure 1, sulfur-containing compound content analyzer includes first be serially connected in appropriate hydrocarbon gas of the present invention
Sample amounts ring 14 and the second sample amounts ring 15, the first sample amounts ring 14 and micro sulfur-containing compound detection unit phase
Even, the micro sulfur-containing compound detection unit include the first split sampling mouth 9 being sequentially connected in series, analysis of sulfur compounds column 4,
Current limliting column 5 and sulphur selective detector 11；The second sample amounts ring 15 is connected with high-concentration sulfur-containing compound test unit,
The high-concentration sulfur-containing compound test unit includes the second split sampling mouth 10, nonpolar capillary chromatographic column 7, flow path switching
Unit, damping column 6, thermal conductivity detector (TCD) 12, polarity capillary chromatographic column 8 and flame ionization ditector 13, described second point
Stream injection port 10 is connect with the nonpolar capillary chromatographic column 7, and the nonpolarity capillary chromatographic column 7 switches with the flow path
The hub-interface of unit is connected, and the interface of flow path switch unit one end and the damping column 6 and the thermal conductivity detector (TCD) 12 are successively
Connection, the interface of the other end are sequentially connected with the polarity capillary chromatographic column 8 and the flame ionization ditector 13.
In the present invention, two sample amounts rings are connected, so that the analysis of sulfur-containing compound in gas is divided into two-way
It carries out, the first via is micro sulfur-containing compound detection unit, uses an analysis of sulfur compounds column and a current limliting column, configuration
Sulphur selective detector detects all sulfur-containing compounds in gas, including hydrogen sulfide, carbonyl sulfur, sulfur dioxide, C1-C5Mercaptan, C1-
C7Thioether, thiophene, thiophane etc., all sulfur-containing compounds can be qualitative, and the detection range of single sulfur-containing compound is 20 × 10-9-100×10-6(volume fraction), the component for being higher than upper limit of detection can only be qualitative, can not quantitative result；Second tunnel
For high-concentration sulfur-containing compound test unit, the sulfurated hydrogen detection in gas is matched using nonpolar capillary chromatographic column with damping column
Thermal conductivity detector (TCD) completion is set, high concentration methyl mercaptan, ethyl mercaptan detection pass through nonpolar capillary chromatographic column, polarity capillary chromatography
Column and flame ionization ditector are completed, wherein nonpolar capillary chromatographic column and damping column and polarity capillary chromatographic column it
Between switching using flow path switch unit complete.
In the preferred case, the first sample amounts ring 14 and the second sample amounts ring 15 are led to by two six cuts
Change valve series connection, series connection method are as follows: four interfaces of the one or six direction changeover valve 1 access the first sample amounts ring 14, and the first sample is fixed
The input end of amount ring 14 is connected with sample introduction pipeline 16, and outlet end is connected with the two or six direction changeover valve 2, as the second sample amounts ring
15 input end, four interfaces of the two or six direction changeover valve 2 access the second sample amounts ring 15, and the second sample amounts ring 15 goes out
Mouth end is connected with blow-down pipe 20.Using six direction changeover valves by pipeline branch in the present invention, six direction changeover valve only has open and close
Two kinds of connection status can will be divided into two-way by the gas of valve, when six-way valve is in a position, flow through the gas of valve along one
A direction flowing, rotates the position of valve, and gas is then flowed along another direction, so as to flow into valve by the position for changing valve
Gas be divided into two kinds of operating conditions.One kind is for the sample introduction into quantitative loop, and another kind is for being passed through the load for carrying sample and being detected
Gas.The carrier gas is preferably helium.
In the present invention, the micro sulfur-containing compound detection unit and the high-concentration sulfur-containing compound analyte detection
Unit is connected with carrier gas line, carries sample flow by carrier gas, i.e., accesses carrier gas line in the upstream of sample amounts ring, make to carry
Gas enters sample amounts ring, carries sample therein and flows through each analytical column and enter back into detector and is detected.
The carrier gas inlet of the micro sulfur-containing compound detection unit connects on the one or six direction changeover valve 1, carrier gas outlet according to
Secondary series connection the first split sampling mouth 9, analysis of sulfur compounds column 4 and sulphur selective detector 11, in order to analyze sulfur-containing compound
The carbonyl sulfur and sulfur dioxide that analytical column 4 can not separate concatenate current limliting column 5 after analysis of sulfur compounds column 4.In a kind of tool
In body embodiment, four interfaces of the one or six direction changeover valve 1 access the first sample amounts ring 14, and remaining two adjacent
Mouth is connected, and an interface is connected to the first carrier gas line 17, another interface is connected with the first split sampling mouth 9.
Carrier gas inlet in the high-concentration sulfur-containing compound test unit connects on the two or six direction changeover valve 2, and carrier gas goes out
Mouth is sequentially connected in series the second split sampling mouth 10, nonpolar capillary chromatographic column 7 and flow path switch unit, passes through flow path switch unit
Gas circuit is divided into two-way, is sequentially connected in series damping column 6 and thermal conductivity detector (TCD) 12 all the way, for analyzing high-concentration hydrogen sulfide, another way
It is sequentially connected in series polarity capillary chromatographic column 8 and flame ionization ditector 13, for analyzing high concentration methyl mercaptan and ethyl mercaptan.
In a specific embodiment, four interfaces of the two or six direction changeover valve 2 access the second sample amounts ring 15, residue two
A adjacent interface is connected, and an interface is connected to the second carrier gas line 21, another interface and the second split sampling mouth
10 are connected.
In the present invention, high-concentration sulfur-containing compound test unit contains three root chromatogram columns and two kinds of detectors, non-pole therein
Property capillary chromatographic column 7 and other two root chromatogram column between connection switching using flow path switch unit complete.The flow path is cut
Change unit optionally by nonpolar capillary chromatographic column 7 different time successively with damping column or nonpolar capillary chromatography
Column is connected, so that the hydrogen sulfide, methyl mercaptan and ethyl mercaptan in gas are kept completely separate, and is detected by different detectors.
In the preferred case, the flow path switch unit is microplate flow path heartcut system 23, in the microplate flow path
Heart diced system 23 includes hub-interface 25 and first interface 26 and second interface 27 and fluidic switch 3 positioned at both ends, institute
It states hub-interface 25 to be connected with nonpolar capillary chromatographic column 7, the first interface 26 is connected with damping column 6, and described second connects
Mouth 27 is connected with polarity capillary chromatographic column 8.When the fluidic switch 3 in the open state, hub-interface 25 and described the
Two interfaces 27 are connected.When the fluidic switch 3 is in close state, hub-interface 25 is connected with the first interface 26.
In the micro sulfur-containing compound detection unit, all sulfur-containing compounds are separable, but one pack system is contained
Amount exceeds 100 × 10-6(V/V) component more than cannot quantify.
In the high-concentration sulfur-containing compound test unit, when in appropriate hydrocarbon gas contain high-concentration hydrogen sulfide, methyl mercaptan, second sulphur
When alcohol, contained C in appropriate hydrocarbon gas3、C4Hydro carbons can not separate on nonpolar capillary chromatographic column with methyl mercaptan, ethyl mercaptan, the present invention
In conjunction with flow path switch unit, hydrogen sulfide is analyzed using nonpolar capillary chromatographic column and thermal conductivity detector (TCD), then passes through stream
Road switch unit is concatenated and is carried out using polarity capillary chromatographic column and flame ionization ditector to methyl mercaptan and ethyl mercaptan
Separation and detection.
In high-concentration sulfur-containing compound test unit, sample passes through 10 sample introduction of split sampling mouth, middle and high concentration vulcanization
Hydrogen separates on nonpolar capillary chromatographic column 7 with other components, and fluidic switch is located at closed state, nonpolar capillary at this time
Chromatographic column 7 is connected directly with damping column 6, and then high-concentration hydrogen sulfide is detected by thermal conductivity detector (TCD) 12, is all flowed out to hydrogen sulfide
Afterwards, fluidic switch goes to opening state, and the methyl mercaptan, ethyl mercaptan in sample are in the form of mixed peak from nonpolar capillary chromatographic column 7
Outflow, is separated into polarity capillary chromatographic column 8, is detected by flame ionization ditector.To ethyl mercaptan in nonpolarity
After whole outflows on capillary chromatographic column 7, switch fluidic switch 3 again to closed state, from nonpolar capillary chromatographic column 7
The boiling point of outflow is higher than remaining C of ethyl mercaptan3、C4Hydro carbons again passes by damping column and is detected by thermal conductivity detector (TCD) 12.
In the present invention, the analysis of sulfur compounds column 4 can be nonpolar capillary chromatographic column, preferably coated solid
Determine the capillary chromatographic column that liquid is dimethyl polysiloxane, such as can be DB-1 capillary column.
In the present invention, the current limliting column 5 is preferably capillary chromatographic column of the inner wall through processing of deactivating.
In the present invention, the nonpolar capillary chromatographic column 7 can be the nonpolar capillary chromatography of this field routine
Column, preferably coated fixer are the capillary chromatographic column of dimethyl polysiloxane, such as can be DB-1 capillary column.
In the present invention, the damping column 6 is preferably inner wall deactivation quartz column, such as Agilent company can be selected raw
The quartz column of the inner wall deactivation of production.
In the present invention, the polarity capillary chromatographic column 8 is preferably the capillary chromatographic column for loading polar stationary phase, example
It can be such as the CP-LOWOX capillary column or GS-OXYPLOT capillary column of Agilent company production.
The application method of analyzer of the present invention can be with are as follows: concatenated two sample amounts rings are first introduced the sample into,
Then two six direction changeover valves are placed in sample introduction position, at this point, carrying of the sample in the first sample amounts ring 14 in carrier gas
It is lower to enter the first split sampling mouth 9, enter analysis of sulfur compounds column 4 and current limliting column 5, all sulfur-containing compounds in sample later
It is detected by sulphur selective detector.
Meanwhile carrier gas brings the sample in the second sample amounts ring 15 into second split sampling mouth 10, sample initially enters
Nonpolar capillary chromatographic column 7, high-concentration hydrogen sulfide therein are separated on nonpolar capillary chromatographic column 7, at this time microplate
The fluidic switch 3 of flow path heartcut system is in close state, and nonpolar capillary chromatographic column 7 is connected in series with damping column 6, sulphur
Change hydrogen and is sent to the detection of thermal conductivity detector (TCD) 12, after whole outflows of hydrogen sulfide, adjustment fluidic switch 3 is in the open state,
Sample middle and high concentration methyl mercaptan, ethyl mercaptan enter polarity capillary chromatographic column 8 under the carrying of carrier gas, C1-C4 hydrocarbon compound by
It is weaker in retaining, it first flows out, polarity is better than the methyl mercaptan of hydrocarbon component, ethyl mercaptan is segregated into hydrogen fire from hydrocarbon mixture
Flame ionization detector 13 is detected.After ethyl mercaptan all flows out on nonpolar capillary chromatographic column 7, adjustment flow control is opened
It closes 3 to be in close state, remaining hydrocarbon component is still flowed out from nonpolar capillary chromatographic column 7 and detected by thermal conductivity detector (TCD) 12.
After all components detection in gaseous sample, each sulfur-bearing chemical combination in gaseous sample can be calculated by external standard method respectively
The content of object component.The gas surveyed is refinery gas, preferably with C3, C4 hydrocarbon liquefied petroleum gas as main component.
It is detailed to being carried out in gas of the present invention containing wide concentration range sulfur-containing compound composition analyzer below with reference to Fig. 1
Explanation.
Analyzer shown in FIG. 1 include the one or six direction changeover valve 1, the two or six direction changeover valve 2, sulphur selective detector 11,
Flame ionization ditector 13, thermal conductivity detector (TCD) 12, the first split sampling mouth 9, the second split sampling mouth 10, five capillaries
Chromatographic column (i.e. analysis of sulfur compounds column 4, current limliting column 5, damping column 6, nonpolar capillary chromatographic column 7 and polarity capillary color
Compose column 8) and flow path switch unit.Sample introduction pipeline 16 is connected with an interface 113 of the one or six direction changeover valve 1, and adjacent connects
Mouth 112 is connected with the arrival end of the first sample amounts ring 14, and the outlet of the first sample amounts ring 14 terminates at interface 115, adjacent
Another interface 114 be connected with pipeline 18, the other end of pipeline 18 connects with the interface 223 of the two or six direction changeover valve 2, and leads to
Another interface 222 to be crossed to connect with the arrival end of the second sample amounts ring 15, the outlet end of quantitative loop 15 connects with interface 225, with
The adjacent interface 224 of interface 225 accesses blow-down pipe 20.The above connection passes through two six direction changeover valves for the first sample amounts ring
14 and second sample amounts ring 15 be cascaded.Each switching valve is divided into two kinds of operating conditions by empty, solid line, and dotted line is valve
In " opening " state, solid line is that valve is in "Off" state.
One or six direction changeover valve 1 interface 111 adjacent with the input end of the first sample amounts ring 14 and 17 phase of carrier gas line
Even, another interface 116 adjacent thereto is connected with the sample introduction part of the first split sampling mouth 9, and the first split sampling mouth 9 goes out
Mouth end is connected with analysis of sulfur compounds column 4, and analysis of sulfur compounds column 4 is connected with current limliting column 5,5 outlet end of current limliting column and sulphur
Selective detector 11 is connected.
The entrance of another way carrier gas line 21 is terminated in the interface end 221 of the two or six direction changeover valve 2, outlet end
226 pass through pipeline 22 and the second split sampling mouth 10 in succession, the outlet of the second split sampling mouth 10 and nonpolar capillary chromatography
Column 7 is connected, and the outlet of nonpolar capillary chromatographic column 7 is connected with the hub-interface 25 of microplate flow path heartcut system 23.It is micro-
The first interface 26 of 23 one end of plate flow path heartcut system is connected with one end of damping column 6, the other end and thermal conductivity of damping column 6
Detector 12 is connected.The second interface 27 of 23 other end of microplate flow path heartcut system and the one of polarity capillary chromatographic column 8
End is connected, and the other end of polarity capillary chromatographic column 8 is connected with flame ionization ditector 13.Microplate flow path heartcut system
The fluidic switch 3 of system 23 divides to open and close two states, and solid line is the closed state of fluidic switch, and dotted line is fluidic switch
Opening state, the driving of fluidic switch controls by gas circuit pipeline 24.
The operating method of analyzer of the present invention is as follows:
The position of two six direction changeover valves is at solid line connection status, i.e. "Off" state in adjustment Fig. 1, makes to analyze
Instrument is in sampling state.Meanwhile microplate flow path heartcut system is in solid line connection status, under test gas passes through sample introduction pipeline
16, the interface 113 of the one or six direction changeover valve and interface 112 enter the first sample amounts ring 14, then from interface 115 and interface 114
Pipeline 18 is flowed through, interface 223 and interface 222 through the two or six direction changeover valve 2 enter the second sample amounts ring 15, then through interface
225 and interface 224 be vented by blow-down pipe 20, carry out sample displacement sampling.
After sampling, micro sulfur compound detection unit and high-concentration sulfur-containing compound test unit are opened, concrete operations are such as
Under:
Micro sulfur-containing compound detection unit: the one or six direction changeover valve 1 and the two or six direction changeover valve 2 are switched to void simultaneously
Line connection status, i.e., " open " state, and analysis instrument starting analysis runs program, the gaseous sample in the first sample amounts ring 14
The carrier gas entered by carrier gas line 17, which is carried, enters the first split sampling mouth 9 by connecting pipeline 19, and gas sample to be measured enters and contains
The current limliting column 5 sulphur compound analytical column 4 (preferably nonpolar capillary chromatographic column) and concatenated therewith, all sulfur-containing compound quilts
Separation, by sulphur selective detector 11, according to setting condition, sulfur-containing compound is detected one by one, and hydrocarbon component is without response.
If there are when high-concentration sulfur-containing compound (hydrogen sulfide, methyl mercaptan, ethyl mercaptan) in sample, analysis of sulfur compounds column
4 can be isolated and be detected by sulphur selective detector 11, but when content exceed detection range when, can not quantitative detection, this hair
It is bright that its content is detected using high-concentration sulfur-containing compound test unit.
High-concentration sulfur-containing compound test unit: the two or six direction changeover valve 2 is in dotted line connection status, and another way carrier gas is logical
It crosses carrier gas line 21 and flows through interface 221 and interface 222, into the second sample amounts ring 15, then carry gaseous sample warp therein
Interface 225 and interface 226 are crossed, the second split sampling mouth 10 is entered by connecting pipeline 22, sample enters nonpolarity after shunting
Capillary chromatographic column 7, since hydrogen sulfide boiling point is minimum, reservation is weaker, flows out first from nonpolar capillary chromatographic column 7, at this time
When the fluidic switch 3 of microplate flow path heartcut system 23 is in solid line connection status, separated by nonpolar capillary chromatographic column 7
High-concentration hydrogen sulfide thermal conductivity detector (TCD) 12 is entered by damping column 6, after hydrogen sulfide is from all outflows of chromatographic column 7, microplate stream
The fluidic switch 3 of road control centre diced system 23 switches to dotted line connection status, to mix peak in nonpolar capillary chromatographic column 7
The boiling point of form outflow is lower than the C of ethyl mercaptan3Hydrocarbon and methyl mercaptan, ethyl mercaptan etc. are transferred to polarity capillary chromatographic column 8, highly concentrated
Degree sulfide is separated from hydrocarbon base, enters the detection of flame ionization ditector 13.When ethyl mercaptan is in nonpolar hair
After all flowing out on capillary chromatographic column 7, the fluidic switch 3 of adjustment microplate flow path heartcut system 23 switches to solid line connection shape
State, sample to be tested mid-boiling point are higher than the C of ethyl mercaptan3、C4The hydrocarbon component continue on nonpolar capillary chromatographic column 7 separation and it is hot
Lead the detection of detector 12.
The present invention is further illustrated below by embodiment, but the present invention is not limited thereto.
Embodiment 1
By Fig. 1 connection chromatographic column and detector, the analysis of sulfur compounds column 4 in micro sulfur-containing compound detection unit is selected
With DB-1 capillary column, column length 60m, column internal diameter 0.53mm；Current limliting column 5 selects capillary chromatography of the inner wall through processing of deactivating
Column, column length 1m, column internal diameter 0.18mm.Nonpolar capillary chromatographic column 7 in high-concentration sulfur-containing compound test unit is selected
DB-1 capillary column, column length 30m, column internal diameter 0.32mm；Polarity capillary chromatographic column 8 selects the CP- of Agilent company production
LOWOX capillary column, column length 10m, column internal diameter 0.53mm；Damping column 6 selects the inner wall deactivation quartz of Agilent company production
Column, column length 0.62m, column internal diameter 0.25mm.
The connecting tube between interface in two six direction changeover valves is all made of 1/16 inch of stainless steel tube, and caliber is indirectly
Head is 1/16 inch.
By above-mentioned six direction changeover valve, microplate flow path control centre diced system, chromatographic column and pipeline by after Fig. 1 connection, press
Condition listed by table 1 analyzes gaseous sample, and the gaseous sample is the liquid containing high-concentration hydrogen sulfide, methyl mercaptan and ethyl mercaptan
Liquefied oil gas sample, gained chromatogram is as in Figure 2-4, and the results are shown in Table 2 for analysis.
Table 1
It infuses, in table 1, for " opening " state of each valve to connect the valve adapter tube line by dotted line, "Off" state is will
The taken over line of the valve is connected by solid line.
Table 2
| Ingredient names | Content, volume fraction × 10-6 |
| Hydrogen sulfide | 5000 |
| Methyl mercaptan | 4900 |
| Ethyl mercaptan | 4800 |
| Dimethyl disulfide | 5 |
| Thiophane | 10 |
| Methylethyl disulfide | 8 |
| Diethyl disulphide | 3 |
| NSC 97324 | 2 |
| Methylethyl trithioether | 1 |
It can be seen that may be implemented to complete by single injected sampling in gas containing wide concentration model using analyzer of the present invention
The qualitative results of sulfur-containing compound are enclosed, and obtain the content of various sulfur-containing compounds accordingly.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. sulfur-containing compound content analyzer in a kind of appropriate hydrocarbon gas, including the first sample amounts ring (14) being serially connected and second
Sample amounts ring (15), the first sample amounts ring (14) are connected with micro sulfur-containing compound detection unit, described micro to contain
Sulphur compound detection unit includes the first split sampling mouth (9), analysis of sulfur compounds column (4), the current limliting column (5) being sequentially connected in series
With sulphur selective detector (11)；The second sample amounts ring (15) is connected with high-concentration sulfur-containing compound test unit, institute
High-concentration sulfur-containing compound test unit is stated to cut including the second split sampling mouth (10), nonpolar capillary chromatographic column (7), flow path
Unit, damping column (6), thermal conductivity detector (TCD) (12), polarity capillary chromatographic column (8) and flame ionization ditector (13) are changed,
The second split sampling mouth (10) connect with the nonpolar capillary chromatographic column (7), the nonpolarity capillary chromatographic column
(7) it is connected with the hub-interface of the flow path switch unit (23), the interface of flow path switch unit one end and the damping column (6)
It is sequentially connected with the thermal conductivity detector (TCD) (12), the interface of the other end and the polarity capillary chromatographic column (8) and hydrogen fire
Flame ionization detector (13) is sequentially connected.
2. analyzer according to claim 1, wherein the first sample amounts ring (14) and second sample amounts
Ring (15) passes through two six direction changeover valves series connection.
3. analyzer according to claim 2, wherein four interfaces of the one or six direction changeover valve (1) access the first sample
The input end of quantitative loop (14), the first sample amounts ring (14) is connected with sample introduction pipeline (16), outlet end and the two or six logical switching
Valve (2) is connected, as the input end of the second sample amounts ring (15), four interfaces access second of the two or six direction changeover valve (2)
The outlet end of sample amounts ring (15), the second sample amounts ring (15) is connected with blow-down pipe (20).
4. analyzer according to claim 2, wherein two adjacent interfaces of the one or six direction changeover valve (1) are connected, and one
A interface is connected to the first carrier gas line (17), another interface is connected with the first split sampling mouth (9)；
Two adjacent interfaces of the two or six direction changeover valve (2) are connected, and an interface is connected to the second carrier gas line (21), another
A interface is connected with the second split sampling mouth (10).
5. analyzer according to claim 1, wherein the flow path switch unit is microplate flow path heartcut system
(23), the microplate flow path heartcut system (23) includes hub-interface (25) and positioned at the first interface (26) at both ends and
Two interfaces (27) and fluidic switch (3), the hub-interface (25) are connected with nonpolar capillary chromatographic column (7), and described the
One interface (26) is connected with damping column (6), and the second interface (27) is connected with polarity capillary chromatographic column (8),
When the fluidic switch (3) in the open state, hub-interface (25) is connected with the second interface (27)；
When the fluidic switch (3) is in close state, hub-interface (25) is connected with the first interface (26).
6. analyzer described in any one of -5 according to claim 1, wherein the analysis of sulfur compounds column (4) is to apply
Stain fixer is the capillary chromatographic column of dimethyl polysiloxane.
7. analyzer described in any one of -5 according to claim 1, wherein the current limliting column (5) is inner wall through deactivating
The capillary chromatographic column of processing.
8. analyzer described in any one of -5 according to claim 1, wherein it is described nonpolarity capillary chromatographic column (7) be
Coated fixer is the capillary chromatographic column of dimethyl polysiloxane.
9. analyzer described in any one of -5 according to claim 1, wherein the damping column (6) is inner wall deactivation quartz
Column.
10. analyzer described in any one of -5 according to claim 1, wherein the polarity capillary chromatographic column (8) is dress
Fill out the capillary chromatographic column of polar stationary phase.
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