CN110895266B - Analysis device and method for measuring content of hydrogen sulfide and phosphine - Google Patents
Analysis device and method for measuring content of hydrogen sulfide and phosphine Download PDFInfo
- Publication number
- CN110895266B CN110895266B CN201911395605.4A CN201911395605A CN110895266B CN 110895266 B CN110895266 B CN 110895266B CN 201911395605 A CN201911395605 A CN 201911395605A CN 110895266 B CN110895266 B CN 110895266B
- Authority
- CN
- China
- Prior art keywords
- hydrogen sulfide
- sample
- phosphine
- detector
- gas device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 111
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 62
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 52
- 238000004458 analytical method Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 77
- 239000012159 carrier gas Substances 0.000 claims abstract description 41
- 238000001514 detection method Methods 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 230000000087 stabilizing effect Effects 0.000 claims description 23
- 238000012937 correction Methods 0.000 claims description 18
- 238000005070 sampling Methods 0.000 claims description 15
- 238000010561 standard procedure Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000005526 G1 to G0 transition Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002737 fuel gas Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000003321 amplification Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000005048 flame photometry Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000007689 inspection Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 3
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000013589 supplement 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
-
- 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
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
- G01N30/8634—Peak quality criteria
-
- 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
- G01N2030/042—Standards
- G01N2030/047—Standards external
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)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Quality & Reliability (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses an analysis device and a method for measuring the content of hydrogen sulfide and phosphine, wherein the device comprises the following components: the device comprises a carrier gas device, a combustion-supporting gas device, a six-way valve, a flame luminosity detector and a display; the carrier gas device is connected to the six-way valve through the first filter; the gas device is connected with the flame luminosity detector through a third filter, the combustion-supporting gas device is connected to the flame luminosity detector through a second filter by two paths of air pipelines, the six-way valve is connected to the chromatographic column, the chromatographic column is connected to the flame luminosity detector, the flame luminosity detector is a double-photomultiplier detector, a sulfur filter and a phosphorus filter are respectively arranged at the outlet of the double-photomultiplier detector, and response signals obtained through detection are respectively connected with the first micro-current amplifier and the second micro-current amplifier and then transmitted to the display for chromatographic spectrogram. The invention can effectively separate hydrogen sulfide and phosphine in the mixed gas and measure the content of the hydrogen sulfide and the phosphine.
Description
Technical Field
The invention relates to an analysis method and a device for measuring the content of hydrogen sulfide and phosphine.
Background
The hydrogen sulfide is colorless, extremely toxic and acid gas, has special odor of the smelly eggs, has unstable chemical property, is easy to decompose when heated, is flammable and has reducibility, and can be easily exploded when being mixed with air or oxygen in a proper proportion (4.3% -4.6%); gaseous phosphine (PH 3) is called phosphine, colorless gas, has characteristic odor of mustard and garlic, has rotten fish-like odor of industrial products, is extremely toxic, and has a lower explosion limit of 1.79% (26 g/m 3) with air mixture. Industries which are easy to generate hydrogen sulfide and phosphine gas are sewage treatment, papermaking, petrochemical industry, chemical fertilizer manufacturing and chemical fiber manufacturing. The content of hydrogen sulfide and phosphine in the air is too high, so that potential explosion safety hazards exist, poisoning accidents can be caused after the hydrogen sulfide is inhaled excessively by a human body, and certain pollution to the environment can be caused by the discharge of the hydrogen sulfide into the atmosphere, such as acid rain, so that the advanced method for detecting the content of the hydrogen sulfide and the phosphine can provide high-efficiency guarantee for the environment, life and production.
Through literature search, the existing method for measuring the contents of hydrogen sulfide and phosphine in domestic industrial gas or atmosphere is different, and the chemical inspection method mainly adopts silver nitrate solution to detect through a colorimetric method, but cannot quantitatively measure the hydrogen sulfide and phosphine component gas. The physical inspection method is mainly gas chromatography, and adopts a pulse flame photometric detector, but only a phosphorus filter is used in the detector for detection, so that the sensitivity of hydrogen sulfide detection is greatly reduced, and the content of hydrogen sulfide cannot be accurately measured.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an analysis device and a method for measuring the content of hydrogen sulfide and phosphine, so as to effectively separate the content of the hydrogen sulfide and the phosphine in industrial gas or atmosphere and accurately measure the content of the hydrogen sulfide and the phosphine.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
The invention relates to an analysis device for measuring the content of hydrogen sulfide and phosphine, which is characterized by comprising the following components: the device comprises a carrier gas device, a combustion-supporting gas device, a six-way valve, a flame luminosity detector and a display;
The carrier gas device is connected to an inlet of the six-way valve through a first filter, a first flow stabilizing valve and a second pressure stabilizing valve are arranged on a pipeline between the first filter and the six-way valve and used for controlling the flow speed and the pressure of the carrier gas device, and the pressure of the carrier gas device is displayed by a first pressure gauge; the outlet of the six-way valve is connected with a flame luminosity detector; a first control valve is arranged on a pipeline between the six-way valve and the flame luminosity detector and used for adjusting the make-up air;
the gas device is connected with the flame luminosity detector through a third filter, and a third flow stabilizing valve and a third pressure stabilizing valve are arranged on a pipeline between the third filter and the flame luminosity FPD detector and used for controlling the flow speed and the pressure of the gas device, and the gas device displays the pressure of the gas device through a third pressure gauge;
The combustion-supporting gas device is divided into two paths of air pipelines after passing through a second filter and is connected to the flame luminosity detector, a second steady flow valve and a second steady pressure valve are arranged on the pipeline between the second filter and the flame luminosity detector and are used for controlling the flow rate and the pressure of the combustion-supporting gas device, the combustion-supporting gas device displays the pressure of the combustion-supporting gas device by a second pressure gauge, and a second control valve and a third control valve are respectively arranged in the two paths of air pipelines;
the outlet of the six-way valve is connected to the inlet of the chromatographic column; the outlet of the chromatographic column is connected to the flame photometric detector;
The flame luminosity detector is a double-photomultiplier detector, and a sulfur filter and a phosphorus filter are respectively arranged at the outlet of the flame luminosity detector and used for completing the detection of hydrogen sulfide and phosphine in a sample to be detected, and the obtained detection response signals are respectively connected with a first micro-current amplifier and a second micro-current amplifier after passing through the first photomultiplier and the second photomultiplier and used for signal amplification, so that the amplified signals are connected to the display and used for obtaining chromatograms.
The analysis device of the invention is also characterized in that: and each pressure stabilizing valve, each flow stabilizing valve, each control valve, each six-way valve and each gas path pipe are made of polytetrafluoroethylene.
The stationary phase filler adopted by the chromatographic column is polymer porous pellets, and the material is quartz glass.
The analysis method of the analysis device for measuring the content of the hydrogen sulfide and the phosphine is characterized by comprising the following steps:
Step 1, calibrating a standard method:
Step 1.1, setting relevant parameters of an analysis device;
Step 1.2, after the device is stabilized, standard gas enters a chromatographic column through the conversion sample injection of the six-way valve under the action of carrier gas N 2 of a carrier gas device, hydrogen sulfide and phosphine in the sample are separated after the sample and a stationary phase are repeatedly adsorbed and desorbed for a plurality of times, and the separated sample flows out of the chromatographic column in sequence according to the size of an adsorption coefficient and flows into a flame luminosity detector;
step 1.3, the flame luminosity detector finishes the detection of the content of hydrogen sulfide and phosphine under the combined action of a sulfur filter, a phosphorus filter, a first photomultiplier and a second photomultiplier, amplifies the generated response value by a first micro-current amplifier and a second micro-current amplifier, and then a chromatogram is formed by a display;
Step 1.4, repeatedly sampling for N times under the same condition, and selecting a group with the best linearity as a calibration standard under the condition that the error is not more than +/-0.2 ppm;
Step 1.5, quantifying by using the peak area, and determining the relative correction factor of hydrogen sulfide and phosphine;
Step2, measuring a sample:
Step 2.1, a sample to be tested in the production process is obtained by using a sampling air bag, and the sampling air bag is replaced by the sample for 2-3 times before sampling;
and 2.2, after the device to be tested is stable, detecting the sample to be tested under the same condition, and after a chromatogram is obtained, detecting the content of hydrogen sulfide and phosphine in the sample to be tested by using a calibrated standard method to obtain an analysis result with the unit of ppm concentration in parts per million.
The analysis method of the invention is also characterized in that: the step 1.1 is carried out according to the following process:
the temperature-raising program of the analysis device is set as follows: the initial temperature is 60 ℃, kept for 2min, and is raised to 130 ℃ at 30 ℃/min, and kept for 3min;
the temperature of the sample injector, namely the six-way valve, is set as follows: 150 ℃;
Setting the temperature of the flame luminosity detector to be: 150 ℃;
the carrier gas of the carrier gas device is high-purity nitrogen, and the carrier gas and carrier gas supplementing air flow rate is set as follows: 30ml/min;
the fuel gas of the fuel gas device is high-purity hydrogen, and the flow rate of the high-purity hydrogen is set as follows: 140ml/min;
the auxiliary fuel gas of the combustion-supporting gas device is air: setting air with different flow rates, wherein one flow rate is as follows: 80ml/min; another flow rate is: 170ml/min.
In the step 1.5, the relative correction factors of hydrogen sulfide and phosphine are determined by using a formula (1):
In the formula (1), the components are as follows, Representing the relative mass correction factor of the component to be measured to the standard; g wi represents the absolute correction factor of the component to be measured; g ws represents the absolute correction factor of the standard component; m i represents the concentration in parts per million of the component to be measured; m s represents the concentration in parts per million of the external standard; a i represents the peak area of the component to be measured; a s represents the peak area of the external standard.
In the step 2.2, the content of hydrogen sulfide and phosphine is obtained by using the formula (2):
in the formula (2), w s represents the mass concentration of the external standard; w i represents the mass concentration of the component to be measured; w s represents the mass of the external standard; w i represents the mass of the component to be measured; a i represents the peak area of the component to be measured; g wi/s represents the relative mass correction factor of the component to be measured to the external standard; k represents the mass fraction of the external standard corresponding to the unit peak area of the external standard, and
Compared with the prior art, the invention has the beneficial effects that:
1. The invention is provided with the double detectors and the inspection method, can measure the accurate concentration of the component to be measured, avoids the error of the chemical analysis method, and has high detection precision and good repeatability.
2. The invention selects the gas chromatograph, the detector adopts flame luminosity sulfur-phosphorus dual detector to measure the content of hydrogen sulfide and phosphine in mixed industrial gas or atmosphere, the operation is simple and convenient, the analysis speed is high, the accuracy of the detection result is high, and the production can be effectively guided in time.
3. The device of the invention avoids volatilization of gas, and the input of chemical reagents and chemical equipment, thereby meeting the requirements of economic operation and environmental protection.
4. The application of the invention not only can improve the analysis speed and ensure the accuracy of the analysis result, but also greatly reduces the consumption of chemical reagents and chemical equipment and the discharge of chemical waste liquid, and meets the national environmental protection requirement while realizing economic operation.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention;
FIG. 2a is a schematic representation of the peaks of a hydrogen sulfide standard gas chromatograph according to the present invention;
FIG. 2b is a schematic representation of the peaks of the phosphine standard gas chromatograph of the present invention;
FIG. 3a is a schematic diagram of chromatographic peaks of a sample to be tested of hydrogen sulfide according to the present invention;
FIG. 3b is a schematic diagram of chromatographic peaks of a sample to be tested of phosphine according to the present invention;
Reference numerals in fig. 1: 1a carrier gas device; 2a combustion-supporting gas device; 3, a gas device; 4a first pressure gauge; 4b a second pressure gauge; 4c a third pressure gauge; 5a first filter; 5b a second filter; 5c a third filter; 6a first flow stabilizing valve; 6b a second flow stabilizing valve; 6c, a third steady flow valve; 7a first pressure stabilizing valve; 7b a second pressure stabilizing valve; 7c a third pressure stabilizing valve; 8 six-way valve; 8a six-way valve inlet; 8b six-way valve outlet; the 8C six-way valve is emptied; 9a first control valve; 9b a second control valve; 9c a third control valve; a 10-column chromatography; 11 flame photometric detector; 12a first photomultiplier tube; 12b a second photomultiplier tube; a 13a sulfur filter; 13b phosphor filters; 14a first micro-current amplifier; 14b a second micro-current amplifier; 15 a display;
Detailed Description
In this embodiment, an analysis device for determining the content of hydrogen sulfide and phosphine is a gas chromatograph, and the detector adopts flame luminosity sulfur-phosphorus dual-filter and dual-photomultiplier detector to determine the content of hydrogen sulfide and phosphine in mixed industrial gas or atmosphere, as shown in fig. 1, the analysis device includes: the device comprises an air path system, a sample injection system, a separation system, a detection system and a display system.
The gas circuit system includes: a carrier gas device 1, a gas device 3 and a combustion-supporting gas device 2;
the carrier gas is filtered by the carrier gas device 1 through the first filter 5a and then is connected to the inlet 8a of the six-way valve 8, and a first steady flow valve 6a and a second steady pressure valve 7a are arranged on a pipeline between the first filter 5a and the six-way valve 8 and are used for controlling the flow rate and the pressure of the carrier gas device 1, and the carrier gas device 1 displays the pressure of the carrier gas device by the first pressure gauge 4a; the outlet 8a of the six-way valve 8 is connected with a flame luminosity detector 11; a make-up gas is arranged on a pipeline between the six-way valve 8 and the flame luminosity detector 11, and a first control valve 9a is arranged for adjusting the make-up gas; after nitrogen (N 2) in the carrier gas device 1 passes through a sample injector, namely a six-way valve 8, the nitrogen is connected with a detector through a control valve 9a to supplement the carrier gas.
The gas device 3 is connected with the flame luminosity detector 11 through a third filter 5c, and a third steady flow valve 6c and a third pressure stabilizing valve 7c are arranged on a pipeline between the third filter 5c and the flame luminosity FPD detector 11 and used for controlling the flow rate and the pressure of the gas device 3, and the gas device 3 displays the pressure by a third pressure gauge 4 c; the hydrogen in the gas device 3 is connected with a Flame Photometric (FPD) detector 11 through a third filter 5c, a third flow stabilizing valve 6c and a third pressure stabilizing valve 7c, and the hydrogen is used as the gas to finish the inspection of the FPD detector on the hydrogen sulfide and the phosphine in the sample.
The gas-assisted device 2 is divided into two paths of air pipelines after being filtered by a second filter 5b and is connected to a flame luminosity detector 11, a second steady flow valve 6b and a second steady pressure valve 7b are arranged on the pipeline between the second filter 5b and the flame luminosity detector 11 and are used for controlling the flow rate and the pressure of the gas-assisted device 2, the pressure of the gas-assisted device 2 is displayed by a second pressure gauge 4b, and a second control valve 9b and a third control valve 9c are respectively arranged in the two paths of air pipelines; the air in the gas-assisted device 2 is divided into two paths by a second filter 5b, a second steady flow valve 6b and a second steady pressure valve 7b, and is controlled by a second control valve 9b and a third control valve 9c to be connected with a flame luminosity (FPD) detector 11, and the FPD detector is assisted by using the air as combustion-supporting gas to finish the measurement of hydrogen sulfide and phosphine in a sample.
The sample injector of the sample injection system is a six-way valve 8; the sample to be measured is converted and sampled through a six-way valve 8, the sample to be measured is accurately measured, and the surplus gas is discharged through the discharge 8c of the six-way valve; the inlet 8a of the six-way valve 8 is connected with the outlet of the carrier gas device 1, and the outlet 8b of the six-way valve 8 is connected to the chromatographic column 10; the inlet of a chromatographic column 10 of the separation system is connected with the outlet of the six-way valve 8, and the outlet of the chromatographic column 10 is connected to a Flame Photometric (FPD) detector 11; the measured sample is brought into a chromatographic column 10 under the action of a mobile phase (carrier gas), the chromatographic column 10 is used for separating two components of hydrogen sulfide and hydrogen phosphide in the sample, and the separated components flow out of the chromatographic column and then enter a flame photometric detector 11;
Wherein, the stationary phase filler adopted by the chromatographic column 10 is polymer porous pellets, and the material is quartz glass, so that the condition of absorbing sulfur (S) in a sample is avoided, and the accuracy of analysis data is improved.
The detection system is a Flame Photometric (FPD) detector 11; the display system is a display 15;
The flame luminosity detector 11 is a double photomultiplier detector, the inlet of the flame luminosity detector 11 is connected with the outlet of the chromatographic column 10, and the outlet of the flame luminosity detector is connected with the first micro-current amplifier 14a and the second micro-current amplifier 14 b;
The outlet of the flame photometry detector 11 is respectively provided with a sulfur filter 13a and a phosphorus filter 13b, so that the first photomultiplier 12a, the second photomultiplier 12b, the sulfur filter 13a and the phosphorus filter 13b are utilized to finish the detection of hydrogen sulfide and phosphine in a sample to be detected, the sulfur and phosphorus electric signals generated by the flame photometry detector 11 are used as detection response signals to be respectively amplified by a first micro-current amplifier 14a and a second micro-current amplifier 14b, the amplified signals are connected to a display 15 for spectral emission of a chromatogram, and finally the content of two components of hydrogen sulfide and phosphine is measured by referring to a calibrated standard method.
The display 15 in the display system is provided with a gas chromatography workstation, and the obtained chromatograms are displayed in the display 15 through the gas chromatography workstation, and are respectively chromatograms of hydrogen sulfide and phosphine standard samples as shown in fig. 2a and 2b, wherein the content of the hydrogen sulfide standard sample in fig. 2a is 280.00ppm, and the content of the phosphine standard sample in fig. 2b is 102.00ppm. According to the standard method for calibrating the content of the standard sample, the standard method is used for measuring the content of the components of the hydrogen sulfide and the hydrogen phosphide in the sample to be tested, and as shown in fig. 3a and 3b, the chromatograms of the hydrogen sulfide and the hydrogen phosphide in the sample to be tested are respectively shown in fig. 3a and 3b, the content of the hydrogen sulfide component in the sample to be tested is 215.30ppm, and the content of the hydrogen phosphide component in the sample to be tested is 11.87ppm in fig. 3 b.
In the specific implementation, each pressure stabilizing valve, each flow stabilizing valve, each control valve, each six-way valve and each gas path pipe are made of polytetrafluoroethylene. The material has high temperature resistance, small adsorption force and extremely low friction coefficient, has acid and alkali resistance, reduces the adsorption of sulfur (S) in a sample, and prolongs the service life of the device;
In the embodiment, an analysis method based on an analysis device for measuring the content of hydrogen sulfide and phosphine is to detect by using a gas chromatograph; the sample to be measured can be mixed industrial gas or atmosphere and the like; and is carried out according to the following steps:
Step 1, calibrating a standard method:
in step 1.1, when the measurement is performed by gas chromatography, relevant parameters of the analysis device are set as follows:
The gas chromatograph is set as follows: SP-3420A;
the detector is set as follows: flame Photometric (FPD) detectors (dual photomultiplier, dual filter);
Setting a chromatographic column as follows: quartz glass column (stationary phase: porous polymer beads);
the temperature-raising program of the analysis device is set as follows: the initial temperature is 60 ℃, kept for 2min, and is raised to 130 ℃ at 30 ℃/min, and kept for 3min;
The temperature of the sample injector, i.e. the six-way valve 8, is set to be: 150 ℃;
the flame photometric detector 11 temperature is set to: 150 ℃;
Setting a hydrogen valve opening control parameter, and opening as follows: 1, a step of; the closing is as follows: 0;
The carrier gas of the carrier gas device 1 is high-purity nitrogen, and the carrier gas and carrier gas supplementing air flow rate is set as follows: 30ml/min;
The gas of the gas device 3 is high-purity hydrogen, and the flow rate of the high-purity hydrogen is set as follows: 140ml/min;
The combustion-supporting gas of the combustion-supporting gas device 2 is air, and air with different flow rates is arranged, wherein one flow rate is as follows: 80ml/min; another flow rate is: 170ml/min.
Step 1.2, adjusting a gas chromatograph according to parameters, after the device is stabilized, standard gas enters a chromatographic column 10 with a stationary phase of high-molecular porous pellets and quartz glass material under the action of carrier gas N 2 of a carrier gas device 1 through conversion sample injection of a six-way valve 8, and after the sample and the stationary phase are repeatedly adsorbed and desorbed for a plurality of times, hydrogen sulfide and phosphine in the sample are separated, and the separated sample flows out of the chromatographic column 10 in sequence according to the size of an adsorption coefficient and flows into a flame luminosity detector 11;
Step 1.3, the flame luminosity detector 11 finishes the detection of the content of hydrogen sulfide and phosphine under the combined action of the sulfur filter 13a, the phosphorus filter 13b, the first photomultiplier 12a and the second photomultiplier 12b, and the generated response value is subjected to amplification treatment of the first micro-current amplifier 14a and the second micro-current amplifier 14b and then is subjected to a chromatographic chart by the display 15;
Step 1.4, repeatedly sampling for N=3 times under the same condition, and selecting a group with the best linearity as a calibration standard under the condition that the error is not more than +/-0.2 ppm;
Step 1.5, the calibration standard method is an external standard method, the peak area is used for quantification, and the relative correction factors of hydrogen sulfide and phosphine are measured; specifically, the relative correction factors of hydrogen sulfide and phosphine are determined by using the formula (1):
In the formula (1), the components are as follows, Representing the relative mass correction factor of the component to be measured to the standard; g wi represents the absolute correction factor of the component to be measured; g ws represents the absolute correction factor of the standard component; m i represents the concentration in parts per million, ppm, of the component to be measured; m s represents the concentration in parts per million, ppm, of the external standard; a i represents the peak area of the component to be measured; a s represents the peak area of the external standard.
Step2, measuring a sample:
Step 2.1, a sample to be tested in the production process is obtained by using a sampling air bag, and the sampling air bag is replaced by the sample for 2-3 times before sampling;
And 2.2, after the gas chromatograph device is stable, detecting the sample to be detected under the same condition, and after the chromatogram is obtained, detecting the content of hydrogen sulfide and hydrogen phosphide in the sample to be detected by using a calibrated standard method to obtain the analysis result with the unit of ppm concentration in parts per million. Specifically, the content of hydrogen sulfide and phosphine is obtained by using the formula (2):
in the formula (2), w s represents the mass concentration of the external standard; w i represents the mass concentration of the component to be measured; w s represents the mass of the external standard; w i represents the mass of the component to be measured; a i represents the peak area of the component to be measured; g wi/s represents the relative mass correction factor of the component to be measured to the external standard; k represents the mass fraction of the external standard corresponding to the unit peak area of the external standard, and
Method repeatability and accuracy test
1. Minimum detection limit test
The mixed industrial gas is selected, the sample is continuously injected for 3 times under the same gas chromatography condition, the measurement is carried out according to a standard gas calibration method, the minimum detection amount is 1.0ppm and 1.6ppm respectively calculated by 3 times of baseline noise.
2. Repeatability test
The standard gas is selected, and is continuously injected for 3 times under the same gas chromatography condition, and the chromatographic peaks of phosphine and hydrogen sulfide three-time injection are used for comparison, and the retention time deviation of the three-time spectrogram is less than 0.1min, so that the method is proved to have good repeatability.
3. Accuracy test
And (3) selecting mixed industrial gas, measuring according to the same gas chromatography condition, repeatedly sampling for 3 times, measuring 3 sampling results by referring to a standard method, and measuring the three sampling results with the up-down deviation of not more than 0.2ppm, so that the method has good accuracy.
Claims (5)
1. An analytical device for determining hydrogen sulfide and phosphine content, comprising: a carrier gas device (1), a gas device (3), a combustion-supporting gas device (2), a six-way valve (8), a flame luminosity detector (11) and a display (15);
The carrier gas device (1) is connected to an inlet (8 a) of the six-way valve (8) through a first filter (5 a), a first flow stabilizing valve (6 a) and a first pressure stabilizing valve (7 a) are arranged on a pipeline between the first filter (5 a) and the six-way valve (8) and are used for controlling the flow rate and the pressure of the carrier gas device (1), and the carrier gas device (1) displays the pressure of the carrier gas device through a first pressure gauge (4 a); the outlet (8 b) of the six-way valve (8) is connected with a flame luminosity detector (11); a first control valve (9 a) is arranged on a pipeline between the six-way valve (8) and the flame luminosity detector (11) and is used for adjusting the make-up air;
The gas device (3) is connected with the flame luminosity detector (11) through a third filter (5 c), a third flow stabilizing valve (6 c) and a third pressure stabilizing valve (7 c) are arranged on a pipeline between the third filter (5 c) and the flame luminosity detector (11) and are used for controlling the flow rate and the pressure of the gas device (3), and the gas device (3) displays the pressure of the gas device through a third pressure gauge (4 c);
The combustion-supporting gas device (2) is divided into two paths of air pipelines after passing through a second filter (5 b) and is connected to the flame luminosity detector (11), a second steady flow valve (6 b) and a second steady pressure valve (7 b) are arranged on the pipeline between the second filter (5 b) and the flame luminosity detector (11) and are used for controlling the flow rate and the pressure of the combustion-supporting gas device (2), the combustion-supporting gas device (2) displays the pressure of the combustion-supporting gas device by a second pressure gauge (4 b), and a second control valve (9 b) and a third control valve (9 c) are respectively arranged in the two paths of air pipelines; the air in the gas-assisted device (2) is divided into two paths by a second filter (5 b), a second flow stabilizing valve (6 b) and a second pressure stabilizing valve (7 b) and is connected with a flame luminosity detector (11) through a second control valve (9 b) and a third control valve (9 c), and the air is used as combustion-supporting gas to assist the flame luminosity detector (11) to finish the measurement of hydrogen sulfide and phosphine in a sample;
The outlet (8 b) of the six-way valve (8) is connected to the inlet of a chromatographic column (10); the outlet of the chromatographic column (10) is connected to the flame photometric detector (11); an inlet (8 a) of the six-way valve (8) is connected with an outlet of the carrier gas device (1), and an outlet (8 b) of the six-way valve (8) is connected to the chromatographic column (10); an inlet of a chromatographic column (10) of the separation system is connected with an outlet of the six-way valve (8), and an outlet of the chromatographic column (10) is connected to a flame luminosity detector (11); the measured sample is brought into a chromatographic column (10) under the action of a mobile phase, the chromatographic column (10) is used for separating two components of hydrogen sulfide and hydrogen phosphide in the sample, and the separated components flow out of the chromatographic column and then enter a flame luminosity detector (11);
The flame luminosity detector (11) is a double-photomultiplier detector, and a sulfur filter (13 a) and a phosphorus filter (13 b) are respectively arranged at the outlet of the flame luminosity detector, and are used for detecting hydrogen sulfide and phosphine in a sample to be detected, and the obtained detection response signals are respectively connected with a first micro-current amplifier (14 a) and a second micro-current amplifier (14 b) after passing through the first photomultiplier (12 a) and the second photomultiplier (12 b) and are used for signal amplification, so that amplified signals are connected to the display (15) for spectral emission;
each pressure stabilizing valve, the control valve, the six-way valve and the air passage pipe are made of polytetrafluoroethylene;
The chromatographic column (10) adopts a stationary phase filler which is a polymer porous pellet and is made of quartz glass.
2. The analysis method of an analysis apparatus for measuring hydrogen sulfide and phosphine contents according to claim 1, wherein the steps of:
Step 1, calibrating a standard method:
Step 1.1, setting relevant parameters of an analysis device;
step 1.2, after the device to be stabilized, standard gas enters the chromatographic column (10) through the conversion sample injection of the six-way valve (8) under the action of carrier gas N 2 of the carrier gas device (1), hydrogen sulfide and phosphine in the sample are separated after the sample and the stationary phase are repeatedly adsorbed and desorbed for a plurality of times, and the separated sample flows out of the chromatographic column (10) in sequence according to the adsorption coefficient and flows into the flame luminosity detector (11);
Step 1.3, the flame luminosity detector (11) finishes the detection of the content of hydrogen sulfide and phosphine under the combined action of a sulfur filter (13 a), a phosphorus filter (13 b), a first photomultiplier (12 a) and a second photomultiplier (12 b), and the generated response value is amplified by a first micro-current amplifier (14 a) and a second micro-current amplifier (14 b) and then a chromatogram is formed by a display (15);
Step 1.4, repeatedly sampling for N times under the same condition, and selecting a group with the best linearity as a calibration standard under the condition that the error is not more than +/-0.2 ppm;
Step 1.5, quantifying by using the peak area, and determining the relative correction factor of hydrogen sulfide and phosphine;
Step2, measuring a sample:
Step 2.1, a sample to be tested in the production process is obtained by using a sampling air bag, and the sampling air bag is replaced by the sample for 2-3 times before sampling;
and 2.2, after the device to be tested is stable, detecting the sample to be tested under the same condition, and after a chromatogram is obtained, detecting the content of hydrogen sulfide and phosphine in the sample to be tested by using a calibrated standard method to obtain an analysis result with the unit of ppm concentration in parts per million.
3. The method of analysis according to claim 2, wherein: the step 1.1 is carried out according to the following process:
the temperature-raising program of the analysis device is set as follows: the initial temperature is 60 ℃, kept for 2min, and is raised to 130 ℃ at 30 ℃/min, and kept for 3min;
the temperature of the sample injector, namely the six-way valve (8), is set as follows: 150 ℃;
Setting the temperature of the flame photometry detector (11) to be: 150 ℃;
the carrier gas of the carrier gas device (1) is high-purity nitrogen, and the carrier gas and carrier gas supplementing air flow rate is set as follows: 30ml/min;
the fuel gas of the fuel gas device (3) is high-purity hydrogen, and the flow rate of the high-purity hydrogen is set as follows: 140ml/min;
the combustion-supporting gas of the combustion-supporting gas device (2) is air: setting air with different flow rates, wherein one flow rate is as follows: 80ml/min; another flow rate is: 170ml/min.
4. The method of analysis according to claim 2, wherein: in the step 1.5, the relative correction factors of hydrogen sulfide and phosphine are determined by using a formula (1):
(1)
In the formula (1), the components are as follows, Representing the relative mass correction factor of the component to be measured to the standard; g wi represents the absolute correction factor of the component to be measured; g ws represents the absolute correction factor of the standard component; m i represents the concentration in parts per million of the component to be measured; m S represents the concentration in parts per million of the external standard; a i represents the peak area of the component to be measured; a S represents the peak area of the external standard.
5. The method of analysis according to claim 2, wherein: in the step 2.2, the content of hydrogen sulfide and phosphine is obtained by using the formula (2):
(2)
In the formula (2), w S represents the mass concentration of the external standard; w i represents the mass concentration of the component to be measured; w s represents the mass of the external standard; w i represents the mass of the component to be measured; a i represents the peak area of the component to be measured; representing the relative quality correction factor of the component to be measured to the external standard; k represents the mass fraction of the external standard corresponding to the unit peak area of the external standard, and/> 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911395605.4A CN110895266B (en) | 2019-12-30 | 2019-12-30 | Analysis device and method for measuring content of hydrogen sulfide and phosphine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911395605.4A CN110895266B (en) | 2019-12-30 | 2019-12-30 | Analysis device and method for measuring content of hydrogen sulfide and phosphine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110895266A CN110895266A (en) | 2020-03-20 |
| CN110895266B true CN110895266B (en) | 2024-05-31 |
Family
ID=69787913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911395605.4A Active CN110895266B (en) | 2019-12-30 | 2019-12-30 | Analysis device and method for measuring content of hydrogen sulfide and phosphine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110895266B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112881365A (en) * | 2021-03-20 | 2021-06-01 | 河南中烟工业有限责任公司 | A dust removal heating removes damp device for flame photometer |
| CN113588858B (en) * | 2021-07-28 | 2023-09-19 | 广东中科检测技术股份有限公司 | Combined gas phase analysis equipment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102749391A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for determining content of monomer aromatic hydrocarbons in gasoline through gas chromatography |
| CN102914613A (en) * | 2012-10-15 | 2013-02-06 | 武汉钢铁(集团)公司 | Method for analyzing hydrogen sulfide in coke oven gas |
| CN107255681A (en) * | 2017-06-08 | 2017-10-17 | 内蒙古中煤蒙大新能源化工有限公司 | A kind of quick measure polypropylene electron donor（CMMS）The method of concentration |
| CN110007022A (en) * | 2019-04-11 | 2019-07-12 | 内蒙古蒙维科技有限公司 | The device and method of oxygen, nitrogen and part organic gas content in a kind of measurement gaseous mixture |
| CN211348073U (en) * | 2019-12-30 | 2020-08-25 | 内蒙古蒙维科技有限公司 | Analysis device for measuring contents of hydrogen sulfide and phosphine |
-
2019
- 2019-12-30 CN CN201911395605.4A patent/CN110895266B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102749391A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for determining content of monomer aromatic hydrocarbons in gasoline through gas chromatography |
| CN102914613A (en) * | 2012-10-15 | 2013-02-06 | 武汉钢铁(集团)公司 | Method for analyzing hydrogen sulfide in coke oven gas |
| CN107255681A (en) * | 2017-06-08 | 2017-10-17 | 内蒙古中煤蒙大新能源化工有限公司 | A kind of quick measure polypropylene electron donor（CMMS）The method of concentration |
| CN110007022A (en) * | 2019-04-11 | 2019-07-12 | 内蒙古蒙维科技有限公司 | The device and method of oxygen, nitrogen and part organic gas content in a kind of measurement gaseous mixture |
| CN211348073U (en) * | 2019-12-30 | 2020-08-25 | 内蒙古蒙维科技有限公司 | Analysis device for measuring contents of hydrogen sulfide and phosphine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110895266A (en) | 2020-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Snell et al. | Performance improvements in the determination of mercury species in natural gas condensate using an on-line amalgamation trap or solid-phase micro-extraction with capillary gas chromatography–microwave-induced plasma atomic emission spectrometry | |
| CN110895266B (en) | Analysis device and method for measuring content of hydrogen sulfide and phosphine | |
| CN102590414B (en) | Method for analyzing contents of trace arsine and phosphine in gas-phase propylene by gas chromatograph | |
| US3638396A (en) | Gas chromatograph interfacing system and method | |
| US3790348A (en) | Apparatus for determining the carbon monoxide, methane and total hydrocarbons content in air | |
| CN110320251B (en) | Online detection device and detection method for content of hydrogen sulfide and tetrahydrothiophene in natural gas | |
| CN103336070A (en) | Detection device and method for quantitatively detecting composition of sulfur-containing fault gas in sulfur hexafluoride electrical equipment | |
| CN104007196A (en) | Secondary cold trap enrichment and GC-FID (Gas Chromatography-Flame Ionization Detector) combining device and method for detecting trace hydrogen phosphide | |
| CN211348073U (en) | Analysis device for measuring contents of hydrogen sulfide and phosphine | |
| CN113624860A (en) | Element analysis-mass spectrometry combined system and method for testing trace sulfur isotope | |
| US6474136B1 (en) | Method and apparatus for analyzing impurities in gases | |
| CN111855866A (en) | Method for rapidly determining formaldehyde in tobacco additive | |
| Zuas et al. | Estimating precision and accuracy of GC-TCD method for carbon dioxide, propane and carbon monoxide determination at different flow rate of carrier gas | |
| CN110376324A (en) | Utilize the method and gas chromatograph of flame ionization ditector measurement oxygen concentration | |
| CN210720291U (en) | Gas chromatograph for measuring oxygen concentration by hydrogen flame ionization detector | |
| US20030133836A1 (en) | System for determining total sulfur content | |
| Suh et al. | Direct determination of arsine in gases by inductively coupled plasma–dynamic reaction cell–mass spectrometry | |
| CN114062540A (en) | Method for rapidly measuring impurity gases of oxygen and argon in pure gas | |
| CN209296659U (en) | A kind of analytical equipment for non-methane total hydrocarbons in VOC | |
| CN202903754U (en) | Inlet gas path automatic control structure of flame ionization detector of gas chromatograph | |
| US4426452A (en) | Volatile metal carbonyl analysis | |
| CN102305835B (en) | Method for detecting formic acid by using hydrogen flame ionization detector based on catalytic reduction technology | |
| CN105675740A (en) | Carbon isotope method for tracing aldehyde ketone pollutants | |
| CN110514549A (en) | A kind of rapid detection method of ammonia acetylene mixing Gas content | |
| Zhong et al. | Optimizations of the EA-IRMS system for δ15N analysis of trace nitrogen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |