CN117890492B - Chromatographic Fourier infrared combined analysis system and method - Google Patents
Chromatographic Fourier infrared combined analysis system and method Download PDFInfo
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- CN117890492B CN117890492B CN202311679446.7A CN202311679446A CN117890492B CN 117890492 B CN117890492 B CN 117890492B CN 202311679446 A CN202311679446 A CN 202311679446A CN 117890492 B CN117890492 B CN 117890492B
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- 238000004458 analytical method Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 66
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 55
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000005922 Phosphane Substances 0.000 claims abstract description 44
- 229910000064 phosphane Inorganic materials 0.000 claims abstract description 44
- 230000007246 mechanism Effects 0.000 claims abstract description 31
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 39
- 239000012159 carrier gas Substances 0.000 claims description 13
- 230000014759 maintenance of location Effects 0.000 claims description 11
- 238000004587 chromatography analysis Methods 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- 238000013375 chromatographic separation Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
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Abstract
The invention is applicable to the technical field of high-purity phosphane impurity analysis, and provides a chromatographic Fourier infrared combined analysis system and a method, wherein the chromatographic Fourier infrared combined analysis system comprises the following components: a chromatographic column, a valve switching device, an infrared spectrum detection device and a pressure control device; the pressure control device is communicated with the infrared spectrum detection device and is used for controlling the air pressure in the testing process of the infrared spectrum detection device. According to the chromatographic Fourier infrared combined analysis system provided by the invention, in the flow limiting mechanism, the flow of the passing gas is controlled through the cooperation of the orifice plate and the orifice plate, so that the failure of a stop valve is avoided, and the detection error of an infrared spectrum detection device is caused by the sudden increase of air pressure.
Description
Technical Field
The invention belongs to the technical field of high-purity phosphane impurity analysis, and particularly relates to a chromatographic Fourier infrared combined analysis system and method.
Background
The high-purity phosphane is widely applied to emerging industries such as integrated circuits, LEDs, photovoltaics and the like due to the special photoelectric property of the high-purity phosphane, and is an electron source most important in the P-N junction growth process. Meanwhile, the indium phosphide semiconductor laser prepared by taking high-purity phosphane as a raw material has important application in sensitive industries such as aerospace, satellite remote sensing and the like. Therefore, it is important to ensure the stable quality production of phosphane with high quality, and the analytical detection technology of high-purity phosphane is also required to be continuously advanced.
The Fourier infrared spectrometry is a commonly used spectral analysis method, and the molecular structure and chemical groups of a sample are judged by measuring infrared absorption spectrums of the sample in different wavelength ranges, so that the method has the advantages of high sensitivity, high resolution and the like, and can be used for accurately quantifying under certain conditions. However, when the content of certain components in the sample to be detected is very low, the components and the content of the mixture are very difficult to determine by simply adopting an infrared spectrometry method for analysis and detection. Because the individual component bands in the mixture mix together or the low content component bands are covered by the main component bands, it is difficult to analyze to get the correct results. In a spectrogram obtained by testing high-purity phosphane by using a Fourier infrared spectrometer, a large number of C-H, si-H, ge-H, O-H, S-H, as-H and other spectral peaks possibly existing in a P-H bond interference system are combined with a chromatographic separation system, so that most of main peaks of the phosphane are removed, and chromatographic effluents at other times are led into infrared analysis, so that more accurate impurity analysis results can be obtained.
To avoid the above-mentioned problems, it is necessary to provide a chromatographic fourier infrared combined analysis system and method to overcome the drawbacks of the prior art.
Disclosure of Invention
The invention aims to provide a chromatographic Fourier infrared combined analysis system and a chromatographic Fourier infrared combined analysis method, which aim to solve the problem of how to combine a chromatographic separation system, remove most of main peaks of phosphane, and introduce other chromatographic effluents into infrared analysis to obtain more accurate impurity analysis results.
The invention is realized in that a chromatographic Fourier infrared combined analysis system comprises:
A chromatographic column, a valve switching device, an infrared spectrum detection device and a pressure control device;
The valve switching device comprises a ten-way valve and a six-way valve, wherein the ten-way valve is provided with ten valve ports with the marks from the first valve port to the tenth valve port, the first valve port is connected with a sample injection pipeline, the second valve port is connected with a sample for emptying, the third valve port and the tenth valve port are connected in series with a quantitative ring, the fourth valve port is connected with a chromatographic column inlet, the fifth valve port, the eighth valve port and the ninth valve port are connected in series with a first carrier gas, and the sixth valve port and the seventh valve port are connected in series with a second carrier gas;
The six-way valve is provided with ten valve ports with the marks from eleven to sixteen, the eleven valve ports are connected with a chromatographic column outlet, the twelve valve ports and the thirteenth valve port are connected with a first emptying valve in series, the fifteenth valve port is connected with a second carrier gas, the fifteenth valve port is connected with the fourteenth valve port and the emptying six-way valve, the sixteen valve port is connected with a stainless steel pipeline device in series, and the sixteen valve port is connected with a sample inlet of the infrared spectrum detection device;
The pressure control device is communicated with the infrared spectrum detection device and is used for controlling the air pressure in the testing process of the infrared spectrum detection device.
Further technical scheme still includes temperature control system, temperature control system includes the accuse temperature area, and the accuse temperature area twines in the pipeline outside.
According to a further technical scheme, the pressure control device comprises an air pressure cylinder, the air pressure cylinder is connected with a pipeline, the pipeline is provided with a stop valve, a flow limiting mechanism is connected in the pipeline in a sliding sealing manner, and the flow limiting mechanism can limit air flow when the air pressure is increased;
One side that the flow-limiting mechanism kept away from the pneumatic cylinder is provided with the fixed plate, the fixed plate rotates and is connected with the outlet duct, the outlet duct annular is provided with a plurality of gas outlet, the outside sliding seal of outlet duct is connected with the sliding sleeve, the sliding sleeve outside is connected with the piston board through the bearing rotation, the inner wall sealing connection of piston board and pipeline, be provided with drive assembly between piston board and the flow-limiting mechanism, when atmospheric pressure suddenly increases, the flow-limiting mechanism can drive the sliding sleeve through drive assembly and adjust the flow area of gas outlet.
According to a further technical scheme, the flow limiting mechanism comprises a hole plate, a limiting rod and a first spring;
The hole plate is connected with the hole plate in a sliding mode along the pipeline, the hole plate is fixedly connected with a limiting rod, the limiting rod is connected with a spring blocking seat in a threaded mode, a spring is sleeved outside the limiting rod, and the spring is connected between the hole plate and the spring blocking seat.
According to a further technical scheme, the orifice disc is communicated with a pressure relief hose, the pressure relief hose is communicated to an air storage tank outside the pipeline, and the pressure relief hose is connected with a one-way air outlet valve.
According to a further technical scheme, one face of the pore plate, which faces away from the pore plate, is rotationally connected with a turbofan.
According to a further technical scheme, the transmission assembly comprises a first toothed plate, a second toothed plate, a gear and a second spring;
The first toothed plate is fixedly connected with the hole disc, the second toothed plate is fixedly connected with the piston plate, the gear is rotationally connected with the inner wall of the pipeline, the first toothed plate and the second toothed plate are meshed with the gear, and the second spring is connected between the first toothed plate and the piston plate.
According to a further technical scheme, the air outlet pipe is fixedly connected with the driven wheel, the fixing plate is fixedly connected with the motor, the output shaft of the motor is fixedly connected with the driving wheel, the driving wheel is meshed with the driven wheel, and the air outlet pipe is annularly provided with a plurality of shunt pipes.
According to a further technical scheme, helium is stored in the air pressure cylinder.
The chromatographic Fourier infrared combined analysis method is applied to the chromatographic Fourier infrared combined analysis system and mainly comprises the following steps of:
step (1): feeding the sample from the sample inlet into the dosing ring;
Step (II): ten-way valve action is performed in 0min, and the sample is driven into the chromatographic column by the carrier gas I;
Step (III): impurities with retention time in front of phosphane directly enter an infrared spectrum detection device;
Step (IV): when the time is 1.6min, the six-way valve acts, the main peak of the phosphane flows out from the emptying valve, the six-way valve is reset for 1.95min, and impurities with retention time in front of the phosphane directly enter the infrared spectrum detection device;
Step (five): the pressure control device is used for controlling the air pressure during the test of the infrared spectrum detection device, and the infrared spectrum detection device records the inflow component analysis within 0-3 min.
Compared with the prior art, the invention has the following beneficial effects:
The chromatographic Fourier infrared combined analysis method provided by the invention can be suitable for analysis and detection of impurities in high-purity phosphane, high-purity arsine and other high-purity gases, and has universality; in addition, under the condition that gas impurities cannot be completely separated after passing through a chromatographic column, the quantitative qualitative of chromatographic peak effluent can be realized through the qualitative of the position of the Fourier infrared band;
According to the chromatographic Fourier infrared combined analysis system provided by the invention, in the flow limiting mechanism, the flow of the passing gas is controlled through the cooperation of the orifice plate and the orifice plate, so that the failure of a stop valve is avoided, and the detection error of an infrared spectrum detection device is caused by the sudden increase of air pressure;
According to the chromatographic Fourier infrared combined analysis system provided by the invention, when the air pressure in a pipeline suddenly increases, the turbofan drives the orifice plate to rotate, so that the flow area between the orifice plate and the orifice plate is reduced, the air pressure on the other side of the orifice plate is further ensured to be stable, and meanwhile, when the air pressure is further increased, the one-way air outlet valve on the pressure relief hose is conducted, and then part of air is led out from the pressure relief hose to the air storage tank outside the pipeline; meanwhile, the hole plate and the hole plate are matched to guide and disperse air flow, so that unstable air pressure in the infrared spectrum detection device caused by overlarge local air flow is avoided;
according to the chromatographic Fourier infrared combined analysis system provided by the invention, the hole plate slides in the pipeline under the action of gas pressure, the piston plate drives the sliding sleeve to adjust the flow area of the gas outlet, so that the gas flow passing through the flow limiting mechanism is further limited when passing through the gas outlet, and the gas pressure stability of the infrared spectrum detection device is ensured;
According to the chromatographic Fourier infrared combined analysis system provided by the invention, the air outlet pipe drives the shunt pipe to rotate, so that the supplementary gas is uniformly dispersed in the infrared spectrum detection device, and detection errors caused by uneven gas distribution in the infrared spectrum detection device are avoided; further, all air outlets on the air outlet pipe rotate, so that air flow at the air inlet end of the air outlet pipe is stably input, and the phenomenon that local air flow is overlarge and unstable is avoided.
Drawings
FIG. 1 is a schematic diagram of a chromatographic Fourier infrared combined analysis system in the invention;
FIG. 2 is a schematic structural diagram of a pressure control device;
FIG. 3 is a cross-sectional view of a conduit;
FIG. 4 is a schematic illustration of the connection of the flow restricting mechanism to the piston plate;
FIG. 5 is a schematic structural view of a flow limiting mechanism;
FIG. 6 is a schematic representation of the retention time of the components on an HP-plot Q column at 50deg.C;
FIG. 7 is a chart of a Fourier infrared spectrum test of high purity phosphane;
FIG. 8 is a high purity phosphane chromatography Fourier infrared combined device chromatography GEH4 standard chart;
FIG. 9 is a high purity phosphane chromatograph-Fourier infrared coupled device chromatograph SiH4 standard chart;
FIG. 10 is a high purity phosphane chromatogram CH4 standard chromatogram of a Fourier infrared combined device;
FIG. 11 is a high purity phosphane chromatography Fourier infrared combined device chromatography CO standard chart;
FIG. 12 is a high purity phosphane chromatography Fourier infrared combined device chromatography CO2 standard chart;
FIG. 13 is a high purity phosphane chromatogram, fourier infrared combination device chromatogram C2H6 standard chart;
FIG. 14 is a high purity phosphane chromatogram, fourier infrared combination device chromatogram C2H4 standard chart.
In the accompanying drawings: 1. an air pressure cylinder; 2. a pipe; 3. a stop valve; 4. a flow restricting mechanism; 41. a hole plate; 42. an orifice plate; 43. a limit rod; 44. a first spring; 45. a spring blocking seat; 5. a fixing plate; 6. a transmission assembly; 61. a first toothed plate; 62. a second toothed plate; 63. a gear; 64. a second spring; 7. an air outlet pipe; 8. an air outlet; 9. a sliding sleeve; 10. a piston plate; 11. a turbofan; 12. driven wheel; 13. a motor; 14. a driving wheel; 15. a shunt; 16. a pressure relief hose; 17. a one-way air outlet valve.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
As shown in fig. 1, the chromatographic fourier infrared combined analysis system provided by the invention comprises:
A chromatographic column, a valve switching device, an infrared spectrum detection device and a pressure control device;
The valve switching device comprises a ten-way valve and a six-way valve, wherein the ten-way valve is provided with ten valve ports with the marks from the first valve port to the tenth valve port, the first valve port is connected with a sample injection pipeline, the second valve port is connected with a sample for emptying, the third valve port and the tenth valve port are connected in series with a quantitative ring, the fourth valve port is connected with a chromatographic column inlet, the fifth valve port, the eighth valve port and the ninth valve port are connected in series with a first carrier gas, and the sixth valve port and the seventh valve port are connected in series with a second carrier gas;
The six-way valve is provided with ten valve ports with the marks from eleven to sixteen, the eleven valve ports are connected with a chromatographic column outlet, the twelve valve ports and the thirteenth valve port are connected with a first emptying valve in series, the fifteenth valve port is connected with a second carrier gas, the fifteenth valve port is connected with the fourteenth valve port and the emptying six-way valve, the sixteen valve port is connected with a stainless steel pipeline device in series, and the sixteen valve port is connected with a sample inlet of the infrared spectrum detection device;
The pressure control device is communicated with the infrared spectrum detection device and is used for controlling the air pressure in the testing process of the infrared spectrum detection device.
In the scheme, the chromatographic Fourier infrared combined analysis system is disclosed, a sample enters a chromatographic column from a quantitative ring, most of phosphane is removed through a valve switching device, other effluents and gas in a pressure control device enter a spectrum chamber together for analysis, namely, a center cutting separation method is adopted according to the retention time of the phosphane, and the analysis detection method can be suitable for analysis detection of impurities in high-purity phosphane, high-purity arsine and other high-purity gases, and has universality and universality. In addition, under the condition that gas impurities cannot be completely separated after passing through a chromatographic column, the quantitative characterization of chromatographic peak effluent can be realized through the Fourier infrared band position characterization by using the chromatographic Fourier infrared combination technology.
As the preferred embodiment of the invention, the chromatographic Fourier infrared combined analysis system further comprises a temperature control system, wherein the temperature control system comprises a temperature control belt which is wound on the outer side of a pipeline, and the temperature control system is further provided with a temperature control device for regulating and controlling the temperature of a chromatographic column, a valve switching device and an infrared spectrum detection device, so that the accuracy of an experimental result is improved;
The pressure control device provides supplementary gas through when infrared spectrum detection device detects to guarantee that pressure stability when infrared spectrum detection device detects, further promote experimental result degree of accuracy, control device can guarantee when the air feed that the air feed air current is stable simultaneously, avoid infrared spectrum detection device to cause experimental result error because instantaneous pressure difference is great, the phosphine is a colorless, extremely toxic, inflammable liquefied compressed gas simultaneously, and pressure stability can guarantee experimental security when control device guarantees to detect.
As a preferred embodiment of the present invention, as shown in fig. 2-5, the pressure control device includes an air pressure cylinder 1, the air pressure cylinder 1 is connected with a pipe 2, the pipe 2 is provided with a stop valve 3, a flow limiting mechanism 4 is connected in a sliding and sealing manner in the pipe 2, and the flow limiting mechanism 4 can limit the air flow when the air pressure increases; one side that the pressure tube 1 was kept away from to current limiter 4 is provided with fixed plate 5, fixed plate 5 rotates and is connected with outlet duct 7, outlet duct 7 annular is provided with a plurality of gas outlet 8, the outside sliding seal of outlet duct 7 is connected with sliding sleeve 9, sliding sleeve 9 outside is connected with piston plate 10 through the bearing rotation, piston plate 10 and the inner wall sealing connection of pipeline 2, be provided with drive assembly 6 between piston plate 10 and the current limiter 4, when the atmospheric pressure suddenly increases, current limiter 4 can drive sliding sleeve 9 through drive assembly 6 and adjust the flow area of gas outlet 8.
In the scheme, before an experiment, a pipeline 2 is connected with an infrared spectrum detection device, when the experiment is performed, a sample enters a chromatographic column from a quantitative ring, most of phosphane is removed through a valve switching device, a stop valve 3 is opened, gas in a gas pressure cylinder 1 passes through a flow limiting mechanism 4, the flow limiting mechanism 4 limits the gas flow, the stop valve 3 is prevented from being invalid, the gas pressure is suddenly increased to cause the detection error of the infrared spectrum detection device, and then the gas passes through a gas outlet 8 on a gas outlet pipe 7 and enters a spectrum chamber together with other effluents in a six-way valve for analysis;
When the air pressure in the pipeline 2 suddenly increases, the flow limiting mechanism 4 can further limit the flow, then the flow limiting mechanism 4 slides in the pipeline 2 under the action of the air pressure, the transmission assembly 6 drives the piston plate 10 to slide in the pipeline 2, and the piston plate 10 drives the sliding sleeve 9 to adjust the flow area of the air outlet 8, so that the air flow passing through the flow limiting mechanism 4 is further limited when passing through the air outlet 8, and the air pressure stability of the infrared spectrum detection device is ensured.
As a preferred embodiment of the present invention, as shown in fig. 5, the flow limiting mechanism 4 includes a hole plate 41, a hole plate 42, a limiting rod 43, and a number one spring 44; the hole plate 41 is in sliding connection along the pipeline 2, the hole plate 42 is in rotary connection with the hole plate 41, the hole plate 42 is fixedly connected with a limiting rod 43, the limiting rod 43 is in threaded connection with a spring blocking seat 45, a first spring 44 is sleeved outside the limiting rod 43, the first spring 44 is connected between the hole plate 41 and the spring blocking seat 45, the hole plate 41 is communicated with a pressure relief hose 16, the pressure relief hose 16 is communicated to an air storage tank outside the pipeline 2, and the pressure relief hose 16 is connected with a one-way air outlet valve 17; the side of the orifice plate 42 facing away from the orifice plate 41 is rotatably connected with the turbofan 11.
In the flow limiting mechanism 4, through the cooperation of the orifice plate 41 and the orifice plate 42, the flow of the passing gas is controlled, when the air pressure is increased, the air pressure pushes the turbofan 11 to rotate, the turbofan 11 drives the orifice plate 42 to rotate, so that the flow area between the orifice plate 42 and the orifice plate 41 is reduced, the air pressure on the other side of the orifice plate 41 is further ensured to be stable, and meanwhile, when the air pressure is further increased, the one-way air outlet valve 17 on the pressure relief hose 16 is conducted, and then part of the air is led out from the pressure relief hose 16 to the air storage tank outside the pipeline 2; meanwhile, the air flow can be guided and dispersed by the cooperation of the orifice plate 41 and the orifice plate 42, so that the unstable air pressure caused by partial air flow is avoided.
As a preferred embodiment of the present invention, as shown in fig. 4, the transmission assembly 6 includes a first toothed plate 61, a second toothed plate 62, a gear 63, and a second spring 64;
The first toothed plate 61 is fixedly connected with the hole plate 41, the second toothed plate 62 is fixedly connected with the piston plate 10, the gear 63 is rotationally connected with the inner wall of the pipeline 2, the first toothed plate 61 and the second toothed plate 62 are meshed with the gear 63, and the second spring 64 is connected between the first toothed plate 61 and the piston plate 10.
In the transmission assembly 6, when the hole plate 41 slides along the pipeline 2, the hole plate 41 drives the first toothed plate 61 to move, the first toothed plate 61 drives the gear 63 to rotate, the gear 63 drives the piston plate 10 to slide in the pipeline 2 through the second toothed plate 62, and the piston plate 10 drives the sliding sleeve 9 to adjust the flow area of the air outlet 8, so that the air flow passing through the flow limiting mechanism 4 is further limited when passing through the air outlet 8, and the air pressure stability of the infrared spectrum detection device is ensured.
As a preferred embodiment of the present invention, as shown in fig. 4, the air outlet pipe 7 is fixedly connected with a driven wheel 12, the fixing plate 5 is fixedly connected with a motor 13, an output shaft of the motor 13 is fixedly connected with a driving wheel 14, the driving wheel 14 is meshed with the driven wheel 12, and the air outlet pipe 7 is annularly provided with a plurality of shunt pipes 15.
The motor 13 is started, the motor 13 drives the driving wheel 14 to rotate, the driving wheel 14 drives the air outlet pipe 7 to rotate through being meshed with the driven wheel 12, and the air outlet pipe 7 drives the shunt pipe 15 to rotate, so that the supplementary air is uniformly dispersed in the infrared spectrum detection device, and detection errors caused by uneven air distribution in the infrared spectrum detection device are avoided; further, all air outlets 8 on the air outlet pipe 7 rotate, so that air flow at the air inlet end of the air outlet pipe 7 is stably input, and unstable air flow caused by overlarge local air flow is avoided.
Helium is stored in the air pressure cylinder 1, and the chemical property of the helium is stable.
Working principle:
Before an experiment, connecting a pipeline 2 with an infrared spectrum detection device, when the experiment is carried out, enabling a sample to enter a chromatographic column from a quantitative ring, removing most of phosphane through a valve switching device, opening a stop valve 3, enabling gas in a gas pressure cylinder 1 to pass through a flow limiting mechanism 4, controlling the flow of the passed gas through the matching of a hole plate 41 and a hole plate 42 in the flow limiting mechanism 4, avoiding the failure of the stop valve 3, enabling the sudden increase of the gas pressure to cause the detection error of the infrared spectrum detection device, and enabling the gas to enter a spectrum room together with other effluents in a six-way valve through a gas outlet 8 on a gas outlet pipe 7 for analysis;
When the air pressure in the pipeline 2 suddenly increases, the air pressure pushes the turbofan 11 to rotate, the turbofan 11 drives the orifice plate 42 to rotate, so that the flow area between the orifice plate 42 and the orifice plate 41 is reduced, the air pressure on the other side of the orifice plate 41 is further ensured to be stable, and meanwhile, when the air pressure is further increased, the one-way air outlet valve 17 on the pressure release hose 16 is conducted, and then part of air is guided out of the air storage tank outside the pipeline 2 by the pressure release hose 16; meanwhile, the air flow can be guided and dispersed by the cooperation of the orifice plate 41 and the orifice plate 42, so that unstable air pressure caused by partial air flow is avoided;
Then the hole plate 41 slides in the pipeline 2 under the pressure of gas, the hole plate 41 drives the first toothed plate 61 to move, the first toothed plate 61 drives the gear 63 to rotate, the gear 63 drives the piston plate 10 to slide in the pipeline 2 through the second toothed plate 62, and the piston plate 10 drives the sliding sleeve 9 to adjust the flow area of the air outlet 8, so that the air flow passing through the flow limiting mechanism 4 is further limited when passing through the air outlet 8, and the air pressure stability of the infrared spectrum detection device is ensured;
The motor 13 is started, the motor 13 drives the driving wheel 14 to rotate, the driving wheel 14 drives the air outlet pipe 7 to rotate through being meshed with the driven wheel 12, and the air outlet pipe 7 drives the shunt pipe 15 to rotate, so that the supplementary air is uniformly dispersed in the infrared spectrum detection device, and detection errors caused by uneven air distribution in the infrared spectrum detection device are avoided; further, all air outlets 8 on the air outlet pipe 7 rotate, so that air flow at the air inlet end of the air outlet pipe 7 is stably input, and unstable air flow caused by overlarge local air flow is avoided.
The chromatographic Fourier infrared combined analysis method is applied to the chromatographic Fourier infrared combined analysis system and mainly comprises the following steps of:
step (1): feeding the sample from the sample inlet into the dosing ring;
Step (II): ten-way valve action is performed in 0min, and the sample is driven into the chromatographic column by the carrier gas I;
Step (III): impurities with retention time in front of phosphane directly enter an infrared spectrum detection device;
Step (IV): when the time is 1.6min, the six-way valve acts, the main peak of the phosphane flows out from the emptying valve, the six-way valve is reset for 1.95min, and impurities with retention time in front of the phosphane directly enter the infrared spectrum detection device;
Step (five): the pressure control device is used for controlling the air pressure during the test of the infrared spectrum detection device, and the infrared spectrum detection device records the inflow component analysis within 0-3 min.
Chromatographic fourier infrared combined analysis method, example 1: and (3) pre-separating the phosphane components by adopting an HP-plot Q series chromatographic column. The chromatographic column has a length of 30m, a diameter of 0.53mm, a film thickness of 20 μm, a column box temperature of 50 ℃, a column inlet flow rate of 60ml/min, an outlet flow rate of 13ml/min, and the main component phosphane is completely emptied through center cutting. The peak time of each component on the column is shown in figure 6. Therefore, ten-way valve operation time (0, 1 min) and six-way valve operation time (1.60, 1.95 min) are set; when the ten-way valve is switched, the carrier gas-sweeps the sample in the quantitative pipe into the chromatographic column; when the six-way valve does not act, the chromatographic column effluent directly enters the infrared spectrum detection device, when the six-way valve acts, the chromatographic column effluent flows to the emptying ten-way valve, namely emptying and center cutting, and when the second action is resetting, the chromatographic column is purged by high-purity carrier gas.
Chromatographic fourier infrared combined analysis method, example 2: according to example 1, the high purity phosphane was subjected to infrared spectroscopic analysis, and chromatographic separation conditions were the same as in example 1 (six-way valve was not actuated, and sample was fully introduced). FIG. 7 is a Fourier infrared spectrum of 99.9999% (6N) high-purity phosphane, and under the condition that main component cutting is not carried out, P-H bonds in a high-concentration phosphane sample occupy the ranges of 800-1400cm < -1 >, 1900-2550cm < -1 >, 3300-3500cm < -1 >, so that qualitative and quantitative determination of other impurity components are seriously interfered.
Chromatographic fourier infrared joint analysis method, example 3: based on the embodiment 1, chromatographic separation conditions are the same as that of the embodiment 1, spectrograms of all components after being subjected to Fourier infrared spectrum analysis by a chromatographic separation system are tested, the components give a spectrum structure diagram on the infrared spectrum along with different retention times, and analysis and detection spectrograms are shown in fig. 8-14. The detection system can complete the separation and analysis of impurities in the phosphane, and has the functions of full spectrum detection, qualitative analysis and the like on the impurities in the high-purity phosphane.
Fourier infrared spectroscopy analysis absorbs impurity molecules in phosphane in the infrared region except symmetrical molecules or molecules with zero dipole moment. And the infrared energy level of the molecule comprises a vibration energy level and a rotation energy level, and a frequency doubling peak and the like exist at the fundamental frequency caused by primary transition or multi-stage transition. The fundamental frequency peak is generally defined as: the molecules absorb infrared rays with a certain frequency, the vibration energy level transits from a ground state to an absorption peak generated by a first vibration excitation state, the peak position of a fundamental frequency peak is equal to the vibration frequency of the molecules or groups, and the intensity is high, so that the infrared absorption peak is the main absorption peak of the infrared rays. And the frequency doubling peak refers to: the absorption peak generated when the vibration level of the molecule transits from the ground state to a high-energy state such as a second vibration excited state and a third vibration excited state is generally weak in intensity.
Fourier infrared spectra identify the absorption peaks present for a functional group from the characteristic peaks, corresponding to the vibrational form of a chemical bond or group in the molecule. The vibration frequency of the same group always appears in a certain area, while the absorption peak of the fingerprint area is characterized by strong characteristics, is highly sensitive to the change of molecular structures, and can distinguish tiny differences in the structures of different compounds. FIG. 7 shows an infrared spectrum of 600-4000cm-1 of phosphane, 850-1350cm-1 of the absorption region exists in the peak of the rotation spectrum of the phosphane molecule, 1950-2550cm-1 of the absorption region exists in the absorption region of the fundamental frequency vibration energy level, and 3200-3600cm-1, 4400-4800cm-1 and other frequency-doubling vibration energy level absorption spectrums exist.
As a preferable scheme of the invention, when the chromatographic Fourier infrared combined analysis system separates impurities in high-purity gas, valve switching programs such as emptying (main peak retention time is at last, main components are led into an emptying valve through a valve switching device after impurity components enter a detection system), back blowing (reverse purging to a chromatographic column through the valve switching device), center cutting (main peak retention time is at last, main components are led into the emptying valve only when main components flow out) and the like can be adopted for analysis and detection of different electronic special gases such as phosphane, arsine and the like.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (6)
1. A chromatographic fourier infrared coupled analysis system, comprising:
A chromatographic column, a valve switching device, an infrared spectrum detection device and a pressure control device;
The valve switching device comprises a ten-way valve and a six-way valve, wherein the ten-way valve is provided with ten valve ports with the marks from the first valve port to the tenth valve port, the first valve port is connected with a sample injection pipeline, the second valve port is connected with a sample for emptying, the third valve port and the tenth valve port are connected in series with a quantitative ring, the fourth valve port is connected with a chromatographic column inlet, the fifth valve port, the eighth valve port and the ninth valve port are connected in series with a first carrier gas, and the sixth valve port and the seventh valve port are connected in series with a second carrier gas;
The six-way valve is provided with ten valve ports with the marks from eleven to sixteen, the eleven valve ports are connected with a chromatographic column outlet, the twelve valve ports and the thirteenth valve port are connected with a first emptying valve in series, the fifteenth valve port is connected with a second carrier gas, the fifteenth valve port is connected with the fourteenth valve port and the emptying six-way valve, the sixteen valve port is connected with a stainless steel pipeline device in series, and the sixteen valve port is connected with a sample inlet of the infrared spectrum detection device;
the pressure control device is communicated with the infrared spectrum detection device and is used for controlling the air pressure in the testing process of the infrared spectrum detection device;
the temperature control system comprises a temperature control belt which is wound on the outer side of the pipeline;
The pressure control device comprises an air pressure cylinder (1), the air pressure cylinder (1) is connected with a pipeline (2), the pipeline (2) is provided with a stop valve (3), a flow limiting mechanism (4) is connected in the pipeline (2) in a sliding sealing manner, and the flow limiting mechanism (4) can limit air flow when the air pressure is increased;
One side of the flow limiting mechanism (4) far away from the air pressure cylinder (1) is provided with a fixed plate (5), the fixed plate (5) is rotationally connected with an air outlet pipe (7), the air outlet pipe (7) is annularly provided with a plurality of air outlets (8), the outside of the air outlet pipe (7) is in sliding sealing connection with a sliding sleeve (9), the outside of the sliding sleeve (9) is rotationally connected with a piston plate (10) through a bearing, the piston plate (10) is in sealing connection with the inner wall of the pipeline (2), a transmission assembly (6) is arranged between the piston plate (10) and the flow limiting mechanism (4), and when the air pressure suddenly increases, the flow limiting mechanism (4) can drive the sliding sleeve (9) to adjust the flow area of the air outlets (8) through the transmission assembly (6);
the flow limiting mechanism (4) comprises a hole plate (41), a hole plate (42), a limiting rod (43) and a first spring (44);
Hole dish (41) are along pipeline (2) sliding connection, orifice plate (42) rotate with hole dish (41) to be connected, orifice plate (42) fixedly connected with gag lever post (43), gag lever post (43) threaded connection has spring to keep off seat (45), gag lever post (43) outside cover is equipped with spring (44), spring (44) connect between hole dish (41) and spring keeps off seat (45), hole dish (41) intercommunication has pressure release hose (16), pressure release hose (16) communicate to the outside gas holder of pipeline (2), pressure release hose (16) are connected with one-way air outlet valve (17).
2. The chromatography-fourier infrared combination analysis system according to claim 1, wherein a turbofan (11) is rotatably connected to a side of the aperture plate (42) facing away from the aperture plate (41).
3. The chromatography fourier infrared combination analysis system according to claim 1, wherein the transmission assembly (6) comprises a first toothed plate (61), a second toothed plate (62), a gear (63) and a second spring (64);
A pinion rack (61) and punch disc (41) fixed connection, no. two pinion rack (62) and piston board (10) fixed connection, gear (63) are connected with the inner wall rotation of pipeline (2), just No. one pinion rack (61) and No. two pinion rack (62) all mesh with gear (63), no. two spring (64) are connected between a pinion rack (61) and piston board (10).
4. The chromatography fourier infrared combined analysis system according to claim 1, wherein the air outlet pipe (7) is fixedly connected with a driven wheel (12), the fixing plate (5) is fixedly connected with a motor (13), an output shaft of the motor (13) is fixedly connected with a driving wheel (14), the driving wheel (14) is meshed with the driven wheel (12), and the air outlet pipe (7) is annularly provided with a plurality of shunt pipes (15).
5. The chromatography fourier infrared combination analysis system according to claim 1, wherein helium is stored in the gas cylinder (1).
6. A method for chromatographic fourier infrared combined analysis applied to the chromatographic fourier infrared combined analysis system according to any one of claims 1 to 5, characterized by comprising the steps of:
step (1): feeding the sample from the sample inlet into the dosing ring;
Step (II): ten-way valve action is performed in 0min, and the sample is driven into the chromatographic column by the carrier gas I;
Step (III): impurities with retention time in front of phosphane directly enter an infrared spectrum detection device;
Step (IV): when the time is 1.6min, the six-way valve acts, the main peak of the phosphane flows out from the emptying valve, the six-way valve is reset for 1.95min, and impurities with retention time in front of the phosphane directly enter the infrared spectrum detection device;
Step (five): the pressure control device is used for controlling the air pressure during the test of the infrared spectrum detection device, and the infrared spectrum detection device records the inflow component analysis within 0-3 min.
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