CN115856186A - Rapid chromatographic separation detection device and detection method for environmental hydrocarbon gas - Google Patents
Rapid chromatographic separation detection device and detection method for environmental hydrocarbon gas Download PDFInfo
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Abstract
The invention discloses a rapid chromatographic separation detection device and a rapid chromatographic separation detection method for environmental hydrocarbon gas, and belongs to the technical field of detection equipment. The device comprises a sampling system, a sample introduction system, a detection system, an auxiliary system and a data processing system; the environmental hydrocarbon gas is extracted and collected by the sampling system; the sampling system is communicated with the sampling system, and the environmental hydrocarbon gas collected by the sampling system is sent to the detection system for separation and detection; the auxiliary system provides carrier gas for the sample injection system and provides combustion gas for the detection system; and the data processing system is connected with the detection system to perform data calculation on the result detected by the detection system, so that the content of the organic matters in the environmental hydrocarbon gas is finally obtained.
Description
Technical Field
The invention relates to the technical field of detection equipment, in particular to a rapid chromatographic separation detection device and a rapid chromatographic separation detection method for environmental hydrocarbon gas.
Background
In the process of environment law enforcement detection and environment emergency monitoring, although the sensor device is quick in response, the problems of low accuracy and easiness in interference exist, and the analysis accuracy is greatly improved due to the prominent separation characteristic of the chromatography.
Traditional laboratory gas chromatograph is when carrying out environmental gas analysis, because the instrument is large-scale and inconvenient portability, often need take into the laboratory gas chromatograph analysis after the on-the-spot sample of gathering, this kind of method has the condensation of sample easily and adsorbs and the long chemical reaction of time, can influence the analysis quantitative effect to the sample.
In recent years, the wide application of portable equipment makes up the defects of the traditional laboratory equipment, but the problems of high power consumption and long separation time still exist.
Therefore, a device and a method for detecting the environmental hydrocarbon gas by flash chromatography are needed to solve the above problems.
Disclosure of Invention
The invention aims to provide a device and a method for detecting the environmental hydrocarbon gas by fast chromatographic separation, which aim to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a rapid chromatographic separation detection device for environmental hydrocarbon gas comprises a sampling system, a sample introduction system, a detection system, an auxiliary system and a data processing system;
the environmental hydrocarbon gas is extracted and collected by the sampling system;
the sampling system is communicated with the sampling system, and the environmental hydrocarbon gas collected by the sampling system is sent to the detection system for separation and detection;
the auxiliary system provides carrier gas for the sample injection system and provides combustion gas for the detection system;
and the data processing system is connected with the detection system to perform data calculation on the result detected by the detection system, so that the content of the organic matters in the environmental hydrocarbon gas is finally obtained.
Through the technical scheme, the content of the environmental hydrocarbon gas can be directly detected on line, so that the accuracy and effectiveness of a detection result are ensured, and the device is small in size, light in weight, portable, handheld, low in power consumption, rapid and stable in separation and strong in anti-interference capacity.
Further, an environmental hydrocarbon gas fast chromatographic fractionation detection device, sampling system includes sampling pump, metal preconcentration pipe and high temperature introduction port, and environmental hydrocarbon gas warp the sampling pump extraction passes through in proper order the high temperature introduction port the metal preconcentration pipe and the sampling pump, wherein the high temperature introduction port temperature keeps 200 ℃ for guarantee the gaseous form of environmental hydrocarbon gas, a stainless steel sintered filter of high temperature introduction port installation for getting rid of macromolecular particulate matter in the environmental hydrocarbon gas, the metal preconcentration pipe adopts Tenax to pack, realizes the gaseous normal atmospheric temperature entrapment of environmental hydrocarbon, heats analytic and desorption function, the sampling pump provides power for extracting environmental hydrocarbon gas.
By adopting the technical scheme, the design of the metal preconcentration tube and low voltage and large current enables the temperature of the metal preconcentration tube to rise to 250 ℃ within 0.5s under the condition of switching on a power supply, and the adsorbed sample is instantly analyzed, so that the focusing degree is high, and the sample introduction speed is high.
Further, the sample injection system comprises a six-way valve, wherein the six-way valve and a pipeline thereof are arranged in a high-temperature valve box, the temperature of the valve box is kept at 160 ℃, and sample injection is realized through switching of the six-way valve.
Further, a gaseous quick chromatographic fractionation detection device of environment hydrocarbon, its characterized in that: the detection system comprises a chromatographic column and a detector, the chromatographic column is communicated with the six-way valve and is used for separating organic matters in the sample gas, and the detector is connected to the outlet end of the chromatographic column so as to detect the separated sample gas;
the chromatographic column is a metal capillary column, and the specification of the chromatographic column is 1m 0.25mm 0.1um.
Through the technical scheme, the metal capillary column is prepared by adopting a micro-processing technology, the volume is smaller, the traditional chromatographic column box part is replaced by a direct heating mode on the metal column, and the power consumption and the volume are reduced to a greater extent; the direct heating is carried out by adopting large current pulses, the pulse frequency and the pulse width are controlled by adopting a rapid PID technology, the temperature programming linearity is good, the repeatability is high, and the error is small.
Further, the quick chromatographic separation detection device for the environmental hydrocarbon gas is characterized in that the detector is a hydrogen flame ionization detector and is provided with an air inlet and a hydrogen inlet;
the data processing system is a data analysis unit and is used for analyzing and calculating the detected result, and the data processing system is characterized in that: under selected operating conditions, after the sample has been vaporized, it is passed through a temperature programmed stainless steel chromatographic column, where the components are separated and detected by a flame ionization detector according to the formula (cx) = cr Ax/Ar where: cx is the sample concentration; cr is the concentration of the reference standard gas; ax is the sample peak area; ar is the standard gas peak area of the control peak. And (4) quantitatively calculating the mass fraction of organic matters in the environmental hydrocarbon gas by using an external standard method.
Further, the detection device comprises an auxiliary system, wherein the auxiliary system comprises a carrier gas pretreatment system, an air pretreatment system and a hydrogen pretreatment system, and the carrier gas pretreatment system is connected to the front end of the carrier gas inlet of the six-way valve so as to pretreat the carrier gas entering the six-way valve; the air pre-treatment system is disposed in front of the air inlet of the detector for pre-treating air entering the detector, and the hydrogen pre-treatment system is disposed in front of the hydrogen inlet of the detector for pre-treating hydrogen entering the detector.
A method for separating and detecting environmental hydrocarbon gas by flash chromatography comprises the following steps:
s1: the high-temperature sample inlet performs high-temperature and filtration pretreatment on the environmental sample gas, and the inside of the valve box is accompanied with heat;
s2: adsorbing the environmental sample gas at normal temperature by the metal preconcentration tube in a sampling state, heating the metal preconcentration tube in a sample introduction state, and quickly thermally desorbing the environmental sample gas into a chromatographic column;
s3: the chromatographic column adopts a direct on-column heating temperature control mode, temperature programming is carried out, and the released environmental sample gas is quickly separated;
s4: the detection system detects the separated environmental sample gas;
s5: and the data processing system performs data processing on the detected result.
Further, the method for rapid chromatographic separation and detection of the environmental hydrocarbon gas has a function of comparing chromatograms, is based on the number of peaks, the height of the peaks and the shape of the peaks, and adopts an algorithm to compare the chromatograms with a built-in standard spectrogram in a similar manner, the algorithm corresponds to the matching degree S between the two spectrograms by calculating cosine similarity, and the calculation method comprises the following steps:
where Ai and Bi are peak areas after normalized calculation of two peaks with the same retention time.
The operator can compare the spectrogram with the stored spectrogram by using the function, the comparison is realized by comparing the complete spectrogram of the unknown substance with the known substance, the unknown substance is confirmed by using a matching degree mode, the known substance is used for defining the unknown substance, the comparison result is displayed in sequence according to the matching degree, when a new spectrogram is exactly and completely matched with the stored spectrogram, the result is displayed as 1.0, when the results are very similar, the result is close to 1.0, and the carbon number and the accurate molecular weight of the pollutant can be visually determined. The method comprises the following steps:
s401: activating a matching spectrum library;
s402: matching and correcting according to the retention time, and judging the consistency of peaks;
s403: running an instrument to analyze unknown substances and displaying a matching degree result;
for step S402, the value may be set to 0.2 to 1.0, with a minimum of 0.6 being suggested, below which the result is not trusted.
Further, the method for detecting the environmental hydrocarbon gas by the rapid chromatographic separation can directly call a related built-in spectrogram or semi-quantitatively refer to response factors of two adjacent substances.
Compared with the prior art, the invention has the following beneficial effects:
1. the rapid chromatographic separation detection device for the environmental hydrocarbon gas, provided by the invention, is provided with the sampling system I, the sample injection system II and the detection system III, so that the environmental hydrocarbon gas can be directly detected on line to obtain the content, the accuracy and the effectiveness of a detection result are ensured, and the rapid chromatographic separation detection device for the environmental hydrocarbon gas is small in size, light in weight, portable, handheld, low in power consumption, rapid and stable in separation and strong in anti-interference capability.
2. The rapid chromatographic separation detection device for the environmental hydrocarbon gas adopts the metal preconcentration tube 2, and the design of low voltage and large current ensures that the metal preconcentration tube 2 can be heated to 250 ℃ within 0.5s under the condition of switching on a power supply, so that an adsorbed sample can be instantly analyzed, the focusing degree is high, and the sample introduction speed is high.
3. The metal capillary column 5 is prepared by adopting a micro-processing technology, the volume is smaller, the traditional chromatographic column box part is replaced by a direct heating mode on the metal column, and the power consumption and the volume are reduced to a greater extent.
4. The metal capillary column 5 is directly heated by using a large current pulse, the pulse frequency and the pulse width are controlled by using a rapid PID technology, and the temperature programming linearity is good, the repeatability is high and the error is small.
5. The device for fast chromatographic separation and detection of the environmental hydrocarbon gas adopts a temperature control technology on the column, the temperature is quickly increased and decreased, and the time precision is greatly improved, so that the identification capability of the half-peak width is improved, the number of column plates is greatly increased, the fast separation is realized, and dozens of hydrocarbons nC 8-nC 40 can be analyzed and detected within 1 min.
6. The rapid chromatographic separation detection device for the environmental hydrocarbon gas can continuously detect the environmental gas in different environments according to actual conditions, so that the detection flexibility and the application range of the rapid chromatographic separation detection device for the environmental hydrocarbon gas are improved.
7. The rapid chromatographic separation detection device for the environmental hydrocarbon gas can ensure that stable carrier gas flows in the chromatographic column no matter which state the six-way valve 4 is switched to, so that the condition that the chromatographic column 5 is burnt out at high temperature in the detection process can be avoided, and the service life of the rapid chromatographic separation detection device for the environmental hydrocarbon gas can be further prolonged.
8. The quick chromatographic separation detection device for the environmental hydrocarbon gas can simultaneously carry out sample introduction and detection, and can detect the content of organic matters in the environmental hydrocarbon gas at one time, so that the quick chromatographic separation detection device for the environmental hydrocarbon gas has a simple structure, is convenient and quick, and has an accurate and reliable detection structure.
9. The rapid chromatographic separation detection device and the detection method for the environmental hydrocarbon gas are simple to operate and easy to operate, so that the operation difficulty is reduced.
10. The rapid chromatographic separation detection device and the detection method for the environmental hydrocarbon gas can perform online detection on the environmental hydrocarbon gas, so that the accuracy of environmental emergency monitoring and environmental law enforcement detection is improved, and the convenience of the detection process is also improved.
11. One advantage of the present invention is to provide a device and a method for rapid chromatographic separation and detection of environmental hydrocarbon gases, wherein the method confirms unknown substances in a matching manner, uses known substances to define unknown substances, can visually determine the carbon number and approximate molecular weight of pollutants, and can invoke a relevant built-in spectrogram or accurately quantitatively analyze by referring to response factors of two adjacent substances, and the device and the method have the advantages of high analysis speed and high accuracy.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of the steps of a rapid chromatographic separation detection device and a detection method for environmental hydrocarbon gas according to the present invention;
FIG. 2 is a schematic structural diagram of an apparatus and a method for rapid chromatographic separation and detection of environmental hydrocarbon gases according to the present invention;
FIG. 3 is a schematic structural diagram of an apparatus and a method for rapid chromatographic separation and detection of environmental hydrocarbon gases according to the present invention;
reference numerals are as follows: 1. a sampling pump; 2. a metal preconcentration tube; 3. a high-temperature sample inlet; 4. a six-way valve; 5. a chromatographic column; 6. a detector; 7. a first flow control system; 8. a first de-hydrocarbon purification system; 9. a carrier gas inlet; 10. a second de-hydrocarbon purification system; 11. a hydrogen inlet; 12. a third hydrocarbon removal purification system; 13. an air inlet; 14. a data analysis unit; i, sampling a system; II, a sample introduction system; III, detecting a system; IV, an auxiliary system; v, a data processing system; a. a gas pathway port; b. a gas pathway port; c. a sample gas inlet; d. a sample gas outlet; e. a carrier gas inlet; f. and a carrier gas outlet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-3, the present invention provides a technical solution: a rapid chromatographic separation detection device for environmental hydrocarbon gas comprises a sampling system, a sample introduction system, a detection system, an auxiliary system and a data processing system;
the environmental hydrocarbon gas can be extracted and collected by a sampling system;
the sampling system is communicated with the sampling system, and the environmental hydrocarbon gas collected by the sampling system is sent to the detection system for separation and detection;
the auxiliary system provides carrier gas for the sample injection system and provides combustion gas for the detection system;
and the data processing system is connected with the detection system to perform data calculation on the detection result of the detection system, so that the content of the organic matters in the environmental hydrocarbon gas is finally obtained.
Through the technical scheme, the content of the environmental hydrocarbon gas can be directly detected on line, so that the accuracy and effectiveness of a detection result are ensured, and the device is small in size, light in weight, portable, handheld, low in power consumption, rapid and stable in separation and strong in anti-interference capacity.
Furthermore, the rapid chromatographic separation detection device for the environmental hydrocarbon gas comprises a sampling pump, a metal preconcentration pipe and a high-temperature sample inlet, wherein the environmental hydrocarbon gas is extracted by the sampling pump and sequentially passes through the high-temperature sample inlet, the metal preconcentration pipe and the sampling pump, the temperature of the high-temperature sample inlet is kept at 200 ℃ for ensuring the gaseous form of the environmental hydrocarbon gas, a stainless steel sintered filter is installed at the high-temperature sample inlet and used for removing macromolecular particles in the environmental hydrocarbon gas, the metal preconcentration pipe adopts Tenax filler, the normal-temperature trapping, heating analysis and desorption functions of the environmental hydrocarbon gas are realized, and the sampling pump provides power for extracting the environmental hydrocarbon gas.
By adopting the technical scheme, the design of the metal preconcentration tube and low voltage and large current enables the temperature of the metal preconcentration tube to rise to 250 ℃ within 0.5s under the condition of switching on a power supply, the adsorbed sample is analyzed instantly, the focusing degree is high, and the sample introduction speed is high.
Furthermore, the rapid chromatographic separation and detection device for the environmental hydrocarbon gas has a stainless steel sintered filter specification of D15 xL 14.3 and a pore size of 70-90um.
Further, the sample injection system comprises a six-way valve, wherein the six-way valve and a pipeline thereof are arranged in a high-temperature valve box, the temperature of the valve box is kept at 160 ℃, and sample injection is realized through switching of the six-way valve.
Further, a gaseous quick chromatographic fractionation detection device of environment hydrocarbon, its characterized in that: the detection system comprises a chromatographic column and a detector, the chromatographic column is communicated with the six-way valve and is used for separating organic matters in the sample gas, and the detector is connected to the outlet end of the chromatographic column so as to detect the separated sample gas;
the column was a metal capillary column and the specification of the column was 1m 0.25mm 0.1um.
Through the technical scheme, the metal capillary column is prepared by adopting a micro-processing technology, the volume is smaller, the traditional chromatographic column box part is replaced by a direct heating mode on the metal column, and the power consumption and the volume are reduced to a greater extent; the direct heating is carried out by adopting large current pulses, the pulse frequency and the pulse width are controlled by adopting a rapid PID technology, the temperature programming linearity is good, the repeatability is high, and the error is small.
Furthermore, the detector is a hydrogen flame ionization detector and is provided with an air inlet and a hydrogen inlet;
the data processing system is a data analysis unit and is used for analyzing and calculating the detected result to obtain the content of the organic matters in the environmental hydrocarbon gas.
Further, the detection device comprises an auxiliary system, wherein the auxiliary system comprises a carrier gas pretreatment system, an air pretreatment system and a hydrogen pretreatment system, and the carrier gas pretreatment system is connected to the front end of the carrier gas inlet of the six-way valve so as to pretreat the carrier gas entering the six-way valve; an air pre-treatment system is disposed in front of the air inlet of the detector to pre-treat air entering the detector, and a hydrogen pre-treatment system is disposed in front of the hydrogen inlet of the detector to pre-treat hydrogen entering the detector.
A quick chromatographic separation and detection method for environmental hydrocarbon gas comprises the following steps:
s1: the high-temperature sample inlet performs high-temperature and filtration pretreatment on the environmental sample gas at 200 ℃, and the inside of the valve box is heated by 160 ℃;
s2: adsorbing the environmental sample gas at normal temperature by the metal pre-concentration tube in a sampling state, heating the metal pre-concentration tube to 250 ℃ in 0.5s in a sampling state, and quickly thermally desorbing the environmental sample gas into a chromatographic column;
s3: the chromatographic column adopts a direct on-column heating temperature control mode, the temperature is programmed to 200 ℃ at the speed of 10 ℃/s, and the released environmental sample gas is rapidly separated;
s4: the detection system detects the separated environmental sample gas;
s5: and the data processing system performs data processing on the detected result.
Further, the detection method has the function of comparing chromatograms, and the method adopts an algorithm to compare the chromatograms with a built-in standard spectrogram on the basis of the number of peaks, the height of the peaks and the shape of the peaks, wherein the algorithm corresponds to the matching degree S between the two spectrograms by calculating the cosine similarity, and the calculation method comprises the following steps:
where Ai and Bi are peak areas after normalized calculation of two peaks with the same retention time.
The operator can compare the spectrogram with the stored spectrogram by using the function, the comparison is realized by comparing the complete spectrogram of the unknown substance with the known substance, the unknown substance is confirmed by using a matching degree mode, the known substance is used for defining the unknown substance, the comparison result is displayed in sequence according to the matching degree, when a new spectrogram is exactly and completely matched with the stored spectrogram, the result is displayed as 1.0, when the results are very similar, the result is close to 1.0, and the carbon number and the accurate molecular weight of the pollutant can be visually determined. The method comprises the following steps:
s401: activating a matching spectrum library;
s402: matching and correcting according to the retention time, and judging the consistency of peaks;
s403: running an instrument to analyze unknown substances and displaying a matching degree result;
for step S402, the value may be set to 0.2 to 1.0, with a minimum of 0.6 being suggested, below which the result is not trusted.
Furthermore, the detection method can directly call a related built-in spectrogram or refer to response factors of two adjacent substances for semi-quantification.
The first embodiment is as follows:
as shown in fig. 2-3, the device for rapid chromatographic separation and detection of environmental hydrocarbon gas comprises a sampling system i, a sampling system ii, a detection system iii, an auxiliary system iv and a data processing system v, wherein the environmental hydrocarbon gas can be extracted and collected by the sampling system i, the sampling system ii is communicated with the sampling system i, and the environmental hydrocarbon gas collected by the sampling system i is sent to the detection system iii for separation and detection, the auxiliary system iv provides carrier gas for the sampling system ii and combustion gas for the detection system iii, and the data processing system v is connected with the detection system iii to perform data calculation on the result detected by the detection system iii, thereby finally obtaining the content of organic matters in the environmental hydrocarbon gas.
Furthermore, the quick chromatographic separation detection device for the environmental hydrocarbon gas is provided with a sampling system I, a sample introduction system II and a detection system III, so that the environmental hydrocarbon gas can be directly detected on line to obtain the content of organic matters in the environmental hydrocarbon gas, and the timeliness of a detection result is ensured.
Furthermore, the sampling system I comprises a sampling pump 1, a metal preconcentration pipe 2 and a high-temperature sample inlet 3, wherein the temperature of the high-temperature sample inlet 3 is kept at 200 ℃ for ensuring the gaseous form of the environmental hydrocarbon gas, and the high-temperature sample inlet 3 is provided with a stainless steel sintered filter for removing macromolecular particles in the environmental hydrocarbon gas.
Further, the sample injection system II comprises a six-way valve 4, wherein the six-way valve 4 and a pipeline thereof are arranged in a high-temperature valve box, the temperature of the valve box is kept at 160 ℃, and sample injection is realized through switching of the six-way valve 4. The six-way valve 4 has 6 valve ports, including a sample gas inlet c, a sample gas outlet b, a carrier gas inlet e, a carrier gas outlet f, and two gas path ports a and d, wherein the sample gas inlet c and the sample gas outlet d are used for the sample gas to enter the six-way valve 4 and exit the six-way valve 4. The metal pre-concentration pipe 2 is connected with the port d and the port a of the six-way valve 4 and is arranged at the outer end of the valve box, so that the sample gas is adsorbed by the metal pre-concentration pipe 2 at normal temperature in the process of passing through the sample gas inlet c and the sample gas outlet b. The carrier gas inlet e and carrier gas outlet f are for the carrier gas to enter the six-way valve 4 and to exit from the six-way valve 4.
Further, in a sampling state, the sampling pump 1 extracts the environmental hydrocarbon gas, the environmental hydrocarbon gas is adsorbed by the metal preconcentration pipe 2 at normal temperature after passing through the high-temperature sample inlet 3, the sample gas inlet c and the gas path port d, and the residual gas is extracted by the sampling pump 1 and then passes through the gas path port a and the sample gas outlet b to reach the gas outlet of the sampling pump 1.
Furthermore, the metal preconcentration tube 2 adopts Tenax packing to realize normal-temperature trapping of the environmental hydrocarbon gas, the temperature of the metal preconcentration tube 2 is raised to 250 ℃ within 0.5s by applying voltage at two ends, the environmental hydrocarbon gas is quickly thermally desorbed and enters the chromatographic column 5, the instantaneity and effectiveness of sampling and sample introduction are ensured, and the power consumption of the instrument is effectively reduced.
Furthermore, the sampling time of the sampling pump 1 can be flexibly configured, for example, the sensitivity can be improved by increasing the pumping time of the sampling pump 1, the sensitivity can be reduced by reducing the pumping time of the sampling pump 1, and the like, and the effectiveness and the saturation of the adsorption of the metal pre-concentration tube 2 are ensured by setting the reasonable pumping time of the sampling pump, so that the amount of the detected environmental hydrocarbon gas and the data accuracy of the final detection result are ensured.
Further, the detection system iii includes a chromatographic column 5 and a detector 6, the chromatographic column 5 is connected to the carrier gas outlet f of the six-way valve 4 and is used for separating organic matters in the sample gas, the detector 6 is connected to the outlet end of the chromatographic column 5, and the carrier gas can enter the six-way valve 4 through the carrier gas inlet e and drive the sample gas to come out from the carrier gas outlet f and sequentially pass through the chromatographic column 5 and the detector 6, so as to detect the organic matters in the sample gas separated by the chromatographic column 5.
Further, the chromatographic column 5 of the ambient hydrocarbon gas flash chromatography separation detection device is implemented as a metal capillary column, and the specification of the chromatographic column 5 is 1m × 0.25mm × 0.1um, and the chromatographic column 5 can completely separate organic matters in the ambient hydrocarbon gas, thereby ensuring the accuracy of the detection result.
Further, the detector 6 is implemented as a hydrogen flame ionization detector 6, and the detector 6 comprises an air inlet 13 and a hydrogen inlet 11, providing an ignition condition for the detector 6.
Further, the data processing system iv of the apparatus for rapid chromatographic separation and detection of environmental hydrocarbon gases according to the present invention is implemented as a data analysis unit 14, the data analysis unit 14 compares the spectrogram with a built-in standard spectrogram by using an algorithm based on the number of peaks, the height of the peaks, and the type of the peaks, the algorithm corresponds to the matching degree S between the two spectrograms by calculating the cosine similarity, and the calculation method thereof is as follows:
where Ai and Bi are peak areas after normalized calculation of two peaks with the same retention time.
Further, the operator can compare the spectrogram with the stored spectrogram by using the function, the comparison is realized by comparing the complete spectrogram of the unknown substance with the known substance, the unknown substance is confirmed by using a matching degree mode, the known substance is used for defining the unknown substance, the comparison result is displayed in sequence according to the matching degree, when a new spectrogram is exactly and completely matched with the stored spectrogram, the result is displayed as 1.0, when the results are very similar, the result is close to 1.0, and the carbon number and the accurate molecular weight of the pollutant can be visually determined.
Further, the data analysis unit 14 can convert the ion current generated by the organic substance in the detector 6 into a software peak, and can directly call a related built-in spectrogram or perform semi-quantitative analysis by referring to response factors of two adjacent substances.
Further, the fast chromatographic separation detection device for the environmental hydrocarbon gas comprises an auxiliary system iv, wherein the auxiliary system iv comprises a carrier gas pretreatment system, an air pretreatment system and a hydrogen pretreatment system, the carrier gas pretreatment system is connected to the front end of the carrier gas inlet e of the six-way valve 4 so as to pretreat the carrier gas entering the six-way valve 4, the air pretreatment system is arranged in front of the air inlet 13 of the detector 6 so as to pretreat the air entering the detector 6, and the hydrogen pretreatment system is arranged in front of the hydrogen inlet 11 of the detector 6 so as to pretreat the hydrogen entering the detector 6.
Further, the carrier gas pretreatment system comprises a carrier gas inlet 9, a first hydrocarbon removal purification system 8 and a first flow control system 7, wherein the first hydrocarbon removal purification system 8 and the first flow control system 7 are sequentially connected behind the carrier gas inlet 9, so that the carrier gas entering the carrier gas inlet 9 is subjected to hydrocarbon removal and the flow is controlled, and the accuracy of the detection result is further ensured.
Further, the hydrogen pretreatment system comprises a hydrogen inlet 11 and a second hydrocarbon removal purification system 10, and the second hydrocarbon removal purification system 10 is connected behind the hydrogen inlet 11 so as to remove hydrocarbons from the hydrogen entering the hydrogen inlet 11, thereby further ensuring the accuracy of the detection result.
Further, the air pretreatment system comprises an air inlet 13 and a third hydrocarbon removal purification system 12, and the third hydrocarbon removal purification system 12 is connected behind the air inlet 13, so that the air entering the air inlet 13 is removed with hydrocarbon by the third hydrocarbon removal purification system 12, and the accuracy of the detection result of the organic matters in the environmental hydrocarbon gas is further ensured.
The second embodiment:
as shown in fig. 1-3, a method for detecting an environmental hydrocarbon gas by fast chromatographic separation is used for detecting the environmental hydrocarbon gas on line, and the method for detecting the environmental hydrocarbon gas on line comprises the following steps:
s1: the high-temperature sample inlet performs high-temperature and filtration pretreatment on the environmental sample gas, and the inside of the valve box is accompanied with heat;
s2: adsorbing the environmental sample gas at normal temperature by the metal preconcentration tube in a sampling state, heating the metal preconcentration tube in a sample introduction state, and quickly thermally desorbing the environmental sample gas into a chromatographic column;
s3: the chromatographic column adopts a direct on-column heating temperature control mode, temperature programming is carried out, and the released environmental sample gas is quickly separated;
s4: the detection system detects the separated environmental sample gas;
s5: and the data processing system performs data processing on the detected result.
In the step S1, the environmental sample gas is pretreated through a high-temperature sample inlet 3; in the step S2, sampling the environmental sample gas through the metal pre-concentration tube 2 and sampling through the six-way valve 4; in step S3, separating the environmental sample gas by the chromatographic column 5 and detecting the environmental sample gas by the detector 6; and in step S4, the detected result is subjected to data processing by the data analysis unit 14.
Next, the operation of the apparatus for rapid chromatographic separation and detection of environmental hydrocarbon gas according to the present invention will be briefly described with reference to fig. 2 and 3.
In a sampling state, the sampling pump 1 extracts the environmental hydrocarbon gas, the environmental hydrocarbon gas is adsorbed by the metal preconcentration pipe 2 at normal temperature after passing through the high-temperature sample inlet 3, the sample gas inlet c and the gas path port d, and the residual gas is extracted by the sampling pump 1 and then passes through the gas path port a, the sample gas outlet b to the gas outlet of the sampling pump 1, so that the sampling process of the environmental hydrocarbon gas is completed.
Meanwhile, the carrier gas sequentially enters the first hydrocarbon removal purification system 8 and the first flow control system 7 through the carrier gas inlet 9 for hydrocarbon removal and quantification, then enters the six-way valve 4 through the carrier gas inlet e of the six-way valve 4, and then exits through the carrier gas outlet f of the six-way valve 4 and enters the chromatographic column 5, so that the chromatographic column 5 is purged, and the chromatographic column 5 is prevented from being burned.
In the detection state, the six-way valve 4 is switched to enable the environment hydrocarbon gas fast chromatographic separation detection device to enter the detection state. The carrier gas enters the first hydrocarbon removal purification system 8 and the first flow control system 7 in sequence through the carrier gas inlet 9 for hydrocarbon removal and quantification, then enters the six-way valve 4 through the carrier gas inlet e of the six-way valve 4, then exits through the gas path port d of the six-way valve 4 and passes through the micro pre-concentration tube 2, at this time, the micro pre-concentration tube 2 is connected with voltage, the temperature rises to 200 ℃ within 0.5s, the adsorbed environmental hydrocarbon gas is subjected to instantaneous thermal desorption, so that the carrier gas drives the environmental hydrocarbon gas in the micro pre-concentration tube 2 and enters the six-way valve 4 again through the gas path port a of the six-way valve 4, finally exits from the six-way valve 4 through the carrier gas outlet f of the six-way valve 4 and enters the chromatographic column 5, at this time, the metal capillary column 5 adopts an on-column direct heating temperature control mode, the temperature is raised to 200 ℃ by a program of 10 ℃/s, the released environmental hydrocarbon gas is rapidly separated, the separated environmental hydrocarbon gas enters the detector 6 for detection, and finally, the detection result is calculated through the data analysis unit 14.
During the detection process, hydrogen enters the detector 6 through the hydrogen inlet 11 and the second hydrocarbon removal purification system 10 in sequence, and air enters the detector 6 through the air inlet 13 and the third hydrocarbon removal purification system 12 in sequence, so that the detector 6 is provided with an ignition condition.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides an environmental hydrocarbon gas flash chromatography separation detection device which characterized in that: the device includes: the system comprises a sampling system, a sample introduction system, a detection system, an auxiliary system and a data processing system;
the environmental hydrocarbon gas is extracted and collected by the sampling system;
the sampling system is communicated with the sampling system, and the environmental hydrocarbon gas collected by the sampling system is sent to the detection system for separation and detection;
the auxiliary system provides carrier gas for the sample introduction system and provides combustion gas for the detection system;
and the data processing system is connected with the detection system to perform data calculation on the result detected by the detection system, so that the content of the organic matters in the environmental hydrocarbon gas is finally obtained.
2. The environmental hydrocarbon gas flash chromatography separation detection apparatus according to claim 1, wherein: sampling system includes that sampling pump, metal preconcentration pipe and high temperature introduction port, and environment hydrocarbon gas warp the sampling pump extraction passes through in proper order the high temperature introduction port the metal preconcentration pipe and the sampling pump, wherein high temperature introduction port temperature keeps 200 ℃ for guarantee the gaseous form of environment hydrocarbon, a high temperature introduction port installation stainless steel sintered filter for getting rid of macromolecular particulate matter in the environment hydrocarbon gas, the metal preconcentration pipe adopts Tenax to pack, realizes gaseous normal atmospheric temperature entrapment, the heating of environment hydrocarbon, analytic and desorption function, the sampling pump provides power for extracting environment hydrocarbon.
3. The apparatus for rapid chromatographic separation and detection of environmental hydrocarbon gases as claimed in claim 2, wherein: the sample injection system comprises a six-way valve, wherein the six-way valve and a pipeline thereof are arranged in a high-temperature valve box, the temperature of the valve box is kept at 160 ℃, and sample injection is realized through switching of the six-way valve.
4. The apparatus for rapid chromatographic separation and detection of environmental hydrocarbon gases as claimed in claim 3, wherein: the detection system comprises a chromatographic column and a detector, wherein the chromatographic column is communicated with the six-way valve and used for separating organic matters in the sample gas, and the detector is connected to the outlet end of the chromatographic column so as to detect the separated sample gas.
5. The apparatus for rapid chromatographic separation and detection of environmental hydrocarbon gases as claimed in claim 4, wherein: the detector is a hydrogen flame ionization detector and has an air inlet and a hydrogen inlet.
6. The data processing system is a data analysis unit and is used for analyzing and calculating the detected result, and the data processing system is characterized in that: under selected working conditions, after a sample is vaporized, each component is separated through a stainless steel chromatographic column with programmed temperature rise, and is detected by a hydrogen flame ionization detector according to a formula (cx) = cr x Ax/Ar; cx is the sample concentration; cr is the concentration of reference standard gas; ax is the sample peak area; ar is the area of the standard gas peak of the reference peak. And (4) quantitatively calculating the mass fraction of organic matters in the environmental hydrocarbon gas by using an external standard method.
7. The separation and detection device for environmental hydrocarbon gas by flash chromatography according to any one of claims 1 to 6, wherein: the detection device comprises an auxiliary system, the auxiliary system comprises a carrier gas pretreatment system, an air pretreatment system and a hydrogen pretreatment system, and the carrier gas pretreatment system is connected to the front end of the carrier gas inlet of the six-way valve so as to pretreat the carrier gas entering the six-way valve; the air pre-treatment system is disposed in front of the air inlet of the detector for pre-treating air entering the detector, and the hydrogen pre-treatment system is disposed in front of the hydrogen inlet of the detector for pre-treating hydrogen entering the detector.
8. A rapid chromatographic separation detection method for environmental hydrocarbon gas is characterized in that: the method comprises the following steps:
s1: the high-temperature sample inlet performs high-temperature and filtration pretreatment on the environmental sample gas, and the inside of the valve box is accompanied with heat;
s2: adsorbing the environmental sample gas at normal temperature by the metal pre-concentration tube in a sampling state, heating the metal pre-concentration tube in a sample introduction state, and quickly thermally desorbing the environmental sample gas into the chromatographic column;
s3: the chromatographic column adopts a direct on-column heating temperature control mode, temperature programming is carried out, and the released environmental sample gas is quickly separated;
s4: the detection system detects the separated environmental sample gas;
s5: and the data processing system performs data processing on the detected result.
9. The method for separating and detecting the environmental hydrocarbon gas by the flash chromatography according to claim 7, which is characterized in that: in step S4, the detection method has a function of comparing chromatograms, and the method compares the chromatograms with a built-in standard spectrogram similarly by using an algorithm based on the number of peaks, the height of peaks, and the pattern of peaks, wherein the algorithm corresponds to the matching degree S between the two spectrograms by calculating the cosine similarity, and the calculation method is as follows:
where Ai and Bi are peak areas after normalized calculation of two peaks with the same retention time.
The operator can compare the spectrogram with the stored spectrogram by using the function, the comparison is realized by comparing the complete spectrogram of the unknown substance with the known substance, the unknown substance is confirmed by using a matching degree mode, the known substance is used for defining the unknown substance, the comparison result is displayed in sequence according to the matching degree, when a new spectrogram is exactly and completely matched with the stored spectrogram, the result is displayed as 1.0, when the results are very similar, the result is close to 1.0, and the carbon number and the accurate molecular weight of the pollutant can be visually determined. The method comprises the following steps:
s401: activating a matching spectrum library;
s402: matching and correcting according to the retention time, and judging the consistency of peaks;
s403: and (5) running the instrument to analyze the unknown substance and displaying a matching degree result.
10. The method for rapid chromatographic separation and detection of environmental hydrocarbon gases according to claim 8, wherein the method comprises the following steps: the detection method can directly call a related built-in spectrogram or perform semi-quantification by referring to response factors of two adjacent substances.
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