CN114755349A - Automatic analysis system and method for low-temperature double-column chromatography of atmospheric volatile organic compounds - Google Patents
Automatic analysis system and method for low-temperature double-column chromatography of atmospheric volatile organic compounds Download PDFInfo
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- CN114755349A CN114755349A CN202210663780.2A CN202210663780A CN114755349A CN 114755349 A CN114755349 A CN 114755349A CN 202210663780 A CN202210663780 A CN 202210663780A CN 114755349 A CN114755349 A CN 114755349A
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- 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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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
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- 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
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- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
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Abstract
The invention discloses a low-temperature double-column chromatographic automatic analysis system and a method for atmospheric volatile organic compounds, wherein the system comprises a signal acquisition processing control unit, a sampling unit, a concentration purification unit, a sample introduction unit, a low-temperature chromatographic separation unit and a detection unit, wherein the sampling unit, the concentration purification unit, the sample introduction unit, the low-temperature chromatographic separation unit and the detection unit are connected with the signal acquisition processing control unit; the atmospheric volatile organic compounds are sequentially controlled to be dehydrated and trapped at low temperature, under given conditions, the adsorption behavior of the target object in the trapping module meets a chromatographic rate equation, no penetration is caused, and the trapping efficiency is about 100%. And after secondary concentration by a low-temperature chromatographic column cold trap, the whole volume is injected into a low-temperature chromatographic column incubator through a Y port, target substances of C2-C12 are separated by two chromatographic columns with different polarities, and qualitative and quantitative analysis is carried out by an FID or MS detector. The method effectively solves the problems that the chromatography drift cannot be accurately determined qualitatively and quantitatively and the like, has the advantages of compact structure, small device, simple operation and reliable result, and is beneficial to practical application and popularization.
Description
Technical Field
The invention relates to the field of chromatographic analysis, in particular to an automatic low-temperature double-column chromatographic analysis system for atmospheric volatile organic compounds.
Background
Volatile Organic Compounds (VOCs) in the atmosphere are organic compounds with high reactivity, can rapidly react with active substances in the atmosphere to generate organic peroxy groups, and further react with NOx in the atmosphere to generate ozone pollution. Part of active volatile organic compounds form secondary organic aerosol through complex processes such as photooxidation and the like, so that the radiation balance is changed, and the climate is influenced.
Because volatile organic compounds in the atmosphere play an important role in the generation of ozone and secondary organic aerosol and are harmful to human health, automatic monitoring and research of the volatile organic compounds in the atmosphere become hot spots in recent years. In recent years, various monitoring devices and methods for measuring volatile organic compounds in the atmosphere have been developed domestically and internationally: one type is equipment for measuring the total amount of volatile organic compounds in atmosphere or pollution source waste gas by a PID detector or an Internet of things system is formed, and the VOCs semi-quantitative result measured by the equipment cannot distinguish the substance types; the second type is a monitoring system which mainly measures volatile organic compounds in the atmosphere by GC-MS or GC-FID and carries out qualitative and quantitative determination on each target component, but the equipment has high price, complex equipment and process and great operation difficulty, is limited by pretreatment, adopts two sets of flow path systems or GC-carried center cutting, measures C2-C4 and C5-C12 components by FID and MS respectively, and has lower time and response resolution ratio and incapability of guaranteeing the data quality effectiveness.
CN104777261A discloses a system, a method and a device for low-temperature gas chromatography of volatile organic compounds in the atmosphere, which completes monitoring of 57 kinds of VOCs. However, the chromatographic system adopts a single chromatographic column and a single detector, and the C2 and C3 partial organic matters can be only analyzed by adopting a low-temperature column incubator at minus 60 ℃, so that the defects of higher cost and easy blockage caused by facing complex practical water-containing samples exist.
CN113311090A provides an online integrated quantitative loop sample feeding monitoring system and a detection method for volatile organic compounds and malodorous substances of a fixed pollution source.
CN112162053A discloses an analyzer and method for multi-component volatile organic compounds, which divide the components to be analyzed of multi-component gases into two groups according to the amount of carbon contained in the gas for analysis.
CN110646549A discloses a thermal desorption instrument, an analysis system and a working method thereof for volatile organic compound detection, wherein center cutting separation C2 and C3 are adopted for FID monitoring, and the rest parts are monitored by MS.
CN107064420A discloses an on-line monitoring system for moderate volatile organic compounds and application thereof.
In the prior art, the analysis problems of C2, C3 and other components are respectively solved by using GC center cutting or two sets of pretreatment flow paths, and the structure is complex and the cost is high; the system for analyzing C2-C12 by using the single column and the single detector can realize the effective separation of the C2 and C3 components only when the temperature of a chromatographic column incubator reaches-60 ℃, and simultaneously, the phenomenon of chromatographic column blockage can be caused due to higher moisture content of an actual sample.
Therefore, the research on the automatic monitoring device is convenient and practical, meets the monitoring and research requirements, and has important significance.
Disclosure of Invention
The invention aims to provide an automatic analysis system for low-temperature double-column chromatography of atmospheric volatile organic compounds, which can realize the rapid detection of the atmospheric volatile organic compounds; by utilizing the preconcentration technology, the low-temperature column incubator technology, the Y-port full-volume sample introduction and double-column double-detector technology, the problems of qualitative and quantitative automatic monitoring of volatile organic compounds in the atmosphere are solved at low cost.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a low-temperature double-column chromatography automatic analysis system for atmospheric volatile organic compounds comprises a signal acquisition processing control unit 16, and a sampling unit 11, a concentration and purification unit 12, a sample introduction unit 13, a low-temperature chromatography separation unit 14 and a detection unit 15 which are connected with the signal acquisition processing control unit 16;
the sampling unit 11 is used for selecting and collecting different types of gas samples, collecting diluted standard gas, internal standard gas, blank nitrogen and actual sample gas according to requirements, and providing a dry blowing gas source;
a concentration purification unit 12 for performing purification treatment of dehydrating, capturing, and removing carbon dioxide interference on the collected gas;
The sample injection unit 13 is used for respectively feeding the target object subjected to thermal analysis into chromatographic columns with different polarities in the same volume according to pressure balance;
a low-temperature chromatographic separation unit 14 for focusing the target object at a low temperature and controlling the programmed temperature rise to make the target object flow into the detection unit 15 one by one;
the detection unit 15 is used for receiving and amplifying a target object signal to form a chromatogram so as to perform qualitative and quantitative analysis;
and the signal acquisition processing control unit 16 is used for being connected with each unit and used for acquiring, processing or reversely controlling the temperature, the pressure and the analog signals of each unit.
Wherein, the concentration and purification unit comprises a dehydration module 201 and a trapping module 202 which are connected with the sample injection unit.
Further optimizing, the sample injection unit comprises a focusing module 301, a silanization Y-port tee 302 and an electronic pressure controller EPC 303, one end of the focusing module 301 is connected with the sample injection unit, the other end of the focusing module 301 is connected with the low-temperature chromatographic separation unit through the silanization Y-port tee 302, and the electronic pressure controller EPC 303 is connected with the sample injection unit.
The low-temperature chromatographic separation unit comprises a chromatographic column A401, a chromatographic column B402, a heat exchanger 403 and a condenser 404, one end of each of the chromatographic column A401 and the chromatographic column B402 is respectively connected with two outlets of the silanization Y-port tee 302, the other end of each of the chromatographic column A401 and the chromatographic column B402 is connected with the detection unit, and the heat exchanger 403 and the condenser 404 form a refrigeration cycle mechanism.
Further defined, the detection unit comprises a detector a 501 and a detector B502, and the detector a 501 and the detector B502 are respectively communicated with the chromatographic column a 401 and the chromatographic column B402.
The sampling unit comprises an eight-in one-out selector valve 101, an eight-way switching valve 102, a silanization three-way valve 103, a sampling flow meter 104, a sampling pump 105, a three-way electromagnetic valve 106, a pressure sensor 107 and a nitrogen sampling flow meter 108;
the eight-in one-out selector valve 101 has S0 bits and S1-8 bits; the S1 bit is a dead plug, the S2 bit is a blowback discharge port, the S3 bit is a standard gas 2, the S4 bit is a standard gas 1, the S5 bit is blank nitrogen, the S6 bit is an internal standard gas, the S7 bit is a sample gas, and the S8 bit is a dead plug;
the eight-way switching valve 102 is provided with a P1-P8 position, a P1 position is connected with an S0 position of the eight-in one-out selector valve 101, a P2 position is connected with an inlet of the dehydration module 201, a P3 position is connected with an inlet of the trapping module 202, a P4 position is connected with an inlet of the focusing module 301, a P5 position is connected with an electronic pressure controller EPC 303, a P6 position is connected with an outlet of the trapping module 202, a P7 position is connected with the silanization tee joint 103, and a P8 position is connected with an outlet of the dehydration module 201;
the nitrogen sampling flow meter 108 is used for being connected with a nitrogen source, the nitrogen sampling flow meter 108 is connected with the three-way electromagnetic valve 106, and two outlets of the three-way electromagnetic valve 106 are respectively communicated with the S5 position and the inlet of the silanization three-way valve 103; a pressure sensor 107 is arranged between the nitrogen sampling flowmeter 108 and the three-way electromagnetic valve 106.
The sampling pump 105 is connected with the silanization tee 103, a sampling flow meter 104 is arranged between the sampling pump 105 and the silanization tee 103, and the end part of the sampling pump 105 is a discharge end.
Further optimizing, the signal acquisition processing control unit comprises temperature and pressure sensors, PID control loops of each temperature control area, and a high-temperature constant-temperature area and a variable-temperature control area which are formed;
the high-temperature constant-temperature area is specifically H1-H7,
wherein:
the eight-in one-out selector valve 101, the eight-way switching valve 102, the silanization tee 103 and the silanization Y-port tee 302 are positioned in an H1 high-temperature constant-temperature area, the S4-7 inlet end is positioned in an H2 high-temperature constant-temperature area, the two ends of the dehydration module 201 are respectively provided with an H3 high-temperature constant-temperature area and an H4 high-temperature constant-temperature area, the two ends of the trapping module 202 are respectively provided with an H5 high-temperature constant-temperature area and an H6 high-temperature constant-temperature area, and the silanization Y-port tee 302 is positioned
The outlet ends are respectively positioned in an H7 high-temperature constant-temperature area;
the temperature-changing control zone is specifically a temperature-changing control zone from T1 to T4;
the dehydration module 201 is located in the temperature swing control zone of T1,
the capture module 202 is located within the temperature swing control zone T2,
the focusing module 301 is located within the temperature swing control zone of T3,
the chromatographic column A401, the chromatographic column B402 and the heat exchanger 403 are all positioned in a temperature-changing control area of T4.
Wherein the dehydration module 201 is a polytetrafluoroethylene hollow pipe with the inner diameter of 2-4 mm and the length of 20-40 cm; the capture module 202 is filled with a quartz liner tube using graphitized carbon black and carbon molecular sieve composite filler as an adsorbent.
Further limiting, H1-H7 are high temperature and constant temperature areas, and are heated by electricity and controlled by PID temperature; T1-T3 are temperature-changing control zones, which are refrigerated and electrically heated by semiconductor elements, and PID controls temperature. T4 is a temperature-changing control zone, and the heat exchanger 403 is arranged in a chromatographic column incubator; the condenser 404 drives the refrigerant, the refrigerant is evaporated and refrigerated in the heat exchanger 403, the refrigerant is heated by the heater in the column oven, and the PID temperature is controlled to 0-5 ℃ as the initial temperature of the chromatogram.
The invention discloses a low-temperature double-column chromatographic automatic analysis method for atmospheric volatile organic compounds, which comprises the following steps:
s1: the system is standby and ready to finish various preparation works before sampling: the temperature and the gas pressure of each temperature control module are included;
s2: collecting gas samples, and collecting different types of gas samples including diluted standard gas, internal standard gas, blank nitrogen and actual sample gas according to set flow rate, volume and different sample channels; and the collected gas sample is dehydrated at low temperature (-45 to-25 ℃) and adsorbed and trapped at low temperature (-45 to-2 ℃);
s3: dry blowing recovery, namely blowing the dehydration module to recover a target object into the capture module by using nitrogen at normal temperature (2-20 ℃), and purifying the capture module to remove carbon dioxide or other interfering substances;
S4: resolving and focusing, wherein the trapping module is heated to the temperature of 250-320 ℃ to resolve the target object, and the target object is carried into a cold trap (-30 to-10 ℃) of the focusing module 301 by carrier gas for secondary concentration and purification;
s5: a Y port is used for sample injection, a cold trap of the focusing module 301 is rapidly heated to 120-200 ℃ for analysis, and the whole volume is equally and respectively fed into two chromatographic columns A401 and B402 with different polarities according to pressure balance;
s6: hot cleaning, a hot cleaning flow path system, a hot cleaning dehydration module 201 and a trapping module 202;
s7: and (3) performing low-temperature chromatographic separation detection, namely performing chromatographic separation treatment in a low-temperature (0-5 ℃) chromatographic column incubator, detecting a separated target object, and analyzing and treating the result.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an integrated preconcentration low-temperature double-column double-detector gas chromatography automatic analysis instrument system for volatile organic compounds in the atmosphere and a working method thereof. Low-temperature trapping concentration, full-volume Y-port sample introduction focusing and low-temperature chromatographic separation detection are adopted, so that the chromatographic separation degree is effectively improved, the qualitative and quantitative stability is enhanced, the detection limit is reduced, and the data quality is guaranteed; PAMS standard chromatograms and degrees of separation are shown in FIGS. 4 and 5.
The linear range of the atmospheric volatile organic compound is 0-10 ppb, and the linear R2 is more than or equal to 0.995; part of the target was linear, see fig. 5.
The detection limit of the method for measuring the atmospheric volatile organic compounds is less than or equal to 0.1ppb, the accuracy is +/-10 percent, and the precision RSD is less than or equal to 10 percent;
the separation degree of cyclopentane and isopentane, the separation degree of 2, 3-dimethylpentane and 2-methylhexane and the separation degree of o-xylene and styrene are more than or equal to 1.0, and the separation degree of PAMS key components is shown in figure 5.
The long-term retention time drift of the invention is less than or equal to 0.2 min.
The invention does not need refrigerant, realizes the low-temperature column temperature box, is suitable for long-term automatic monitoring, has low maintenance amount and low cost, and is convenient, economic and applicable.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is an overall schematic block diagram of the present invention.
FIG. 2 is a block diagram of a testing method according to the present invention.
Fig. 3 is an overall schematic of the present invention.
FIG. 4 is a PAMS standard chromatogram and key component separation chart on a DB-1 chromatographic column of the invention.
FIG. 5 is a PAMS standard chromatogram and key component separation chart on a PLOT-Q chromatographic column of the invention.
FIG. 6 is a line graph of a portion of the PAMS components of the present invention.
FIG. 7 is a SIM spectrum of the selected ion for mass spectrometric detection of organic substances.
Reference numerals are as follows:
11-a sampling unit, 12-a concentration and purification unit, 13-a sample introduction unit, 14-a low-temperature chromatographic separation unit, 15-a detection unit and 16-a signal acquisition and processing control unit; 101-eight-in one-out selector valve, 102-eight-way switching valve, 103-silanization three-way valve, 104-sampling flowmeter, 105-sampling pump, 106-three-way solenoid valve, 107-pressure sensor, 108-nitrogen sampling flowmeter, 301-focusing module, 302-silanization Y-port three-way valve, 303-electronic pressure controller EPC, 401-chromatographic column A, 402-chromatographic column B, 403-heat exchanger, 404-condenser, 501-detector A, 502-detector B.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the embodiments of the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
In the description of the embodiments of the present invention, it should be understood that the terms "length", "vertical", "horizontal", "top", "bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only used for convenience in describing the embodiments of the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the embodiments of the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the embodiments of the present invention, "a plurality" means two or more unless specifically limited otherwise.
In the embodiments of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," "fixed," and the like are to be construed broadly, e.g., as being fixedly connected, detachably connected, or integrated; the connection can be mechanical connection, electrical connection or communication; either directly or indirectly through intervening media, either internally or in any other relationship. Specific meanings of the above terms in the embodiments of the present invention can be understood by those of ordinary skill in the art according to specific situations.
In embodiments of the present invention, unless expressly stated or limited otherwise, the recitation of a first feature "on" or "under" a second feature may include the recitation of the first and second features being in direct contact, and may also include the recitation of the first and second features not being in direct contact, but being in contact with another feature between them. Also, the first feature "on," "above" and "over" the second feature may include the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is at a higher level than the second feature. The first feature being "under," "beneath," and "under" the second feature includes the first feature being directly above and obliquely above the second feature, or simply meaning that the first feature is at a lesser level than the second feature.
The following disclosure provides many different embodiments or examples for implementing different configurations of embodiments of the invention. To simplify the disclosure of embodiments of the invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit embodiments of the invention. Furthermore, embodiments of the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example one
Referring to fig. 1-7, the embodiment discloses an automatic analysis system for low-temperature dual-column chromatography of atmospheric volatile organic compounds, which includes a signal acquisition processing control unit 16, and a sampling unit 11, a concentration and purification unit 12, a sample introduction unit 13, a low-temperature chromatography separation unit 14 and a detection unit 15 connected to the signal acquisition processing control unit 16;
the sampling unit 11 is used for selecting and collecting different types of gas samples, collecting diluted standard gas, internal standard gas, blank nitrogen and actual sample gas according to requirements, and providing a dry blowing gas source;
a concentration purification unit 12 for performing purification treatment of dehydrating, capturing, and removing carbon dioxide interference on the collected gas;
the sample injection unit 13 is used for respectively feeding the target object subjected to thermal analysis into chromatographic columns with different polarities in the same volume according to pressure balance;
a low-temperature chromatographic separation unit 14 for focusing the target object at a low temperature and controlling the programmed temperature rise to make the target object flow into the detection unit 15 one by one;
the detection unit 15 is used for receiving and amplifying a target object signal to form a chromatogram so as to perform qualitative and quantitative analysis;
And the signal acquisition processing control unit 16 is used for being connected with each unit and used for acquiring, processing or reversely controlling the temperature, the pressure and the analog signals of each unit.
The concentration and purification unit 12 includes a dehydration module 201 and a capture module 202 connected to the sample injection unit 13.
Further preferably, the sample injection unit 13 comprises a focusing module 301, a silanization Y-port tee 302 and an electronic pressure controller EPC303, one end of the focusing module 301 is connected with the sample injection unit 13, the other end of the focusing module 301 is connected with the low-temperature chromatography separation unit 14 through the silanization Y-port tee 302, and the electronic pressure controller EPC303 is connected with the sample injection unit 13.
The low-temperature chromatographic separation unit 14 comprises a chromatographic column a401, a chromatographic column B402, a heat exchanger 403 and a condenser 404, one end of each of the chromatographic column a401 and the chromatographic column B402 is respectively connected with two outlets of the silanization Y-port tee 302, the other end of each of the chromatographic column a401 and the chromatographic column B402 is connected with the detection unit 15, and the heat exchanger 403 and the condenser 404 form a refrigeration cycle mechanism.
Further defined, the detection unit 15 comprises a detector a501 and a detector B502, and the detector a501 and the detector B502 are respectively communicated with the chromatographic columns a401 and B402.
The sampling unit 11 comprises an eight-in one-out selector valve 101, an eight-way switching valve 102, a silanization three-way valve 103, a sampling flow meter 104, a sampling pump 105, a three-way electromagnetic valve 106, a pressure sensor 107 and a nitrogen sampling flow meter 108;
The eight-in one-out selector valve 101 has S0 bits and S1-8 bits; the S1 bit is dead block, the S2 bit is a blowback discharge port, the S3 bit is standard gas 2, the S4 bit is standard gas 1, the S5 bit is blank nitrogen, the S6 bit is internal standard gas, the S7 bit is sample gas, and the S8 bit is dead block;
the eight-way switching valve 102 is provided with a P1-P8 position, a P1 position is connected with an S0 position of the eight-in one-out selector valve 101, a P2 position is connected with an inlet of the dehydration module 201, a P3 position is connected with an inlet of the trapping module 202, a P4 position is connected with an inlet of the focusing module 301, a P5 position is connected with an electronic pressure controller EPC303, a P6 position is connected with an outlet of the trapping module 202, a P7 position is connected with the silanization tee joint 103, and a P8 position is connected with an outlet of the dehydration module 201;
the nitrogen sampling flow meter 108 is used for being connected with a nitrogen source, the nitrogen sampling flow meter 108 is connected with the three-way electromagnetic valve 106, and two outlets of the three-way electromagnetic valve 106 are respectively communicated with the S5 position and the inlet of the silanization three-way valve 103; a pressure sensor 107 is arranged between the nitrogen sampling flowmeter 108 and the three-way electromagnetic valve 106.
The sampling pump 105 is connected with the silanization tee 103, a sampling flow meter 104 is arranged between the sampling pump 105 and the silanization tee 103, and the end part of the sampling pump 105 is a discharge end.
The signal acquisition processing control unit 16 comprises a temperature sensor 107, a pressure sensor 107, PID control loops of temperature control areas, a high-temperature constant-temperature area and a variable-temperature control area;
The high-temperature constant-temperature area is specifically H1-H7,
wherein:
the eight-in one-out selector valve 101, the eight-way switching valve 102, the silanization tee 103 and the silanization Y-port tee 302 are positioned in an H1 high-temperature constant-temperature area, the S4-7 inlet end is positioned in an H2 high-temperature constant-temperature area, the two ends of the dehydration module 201 are respectively provided with an H3 high-temperature constant-temperature area and an H4 high-temperature constant-temperature area, the two ends of the trapping module 202 are respectively provided with an H5 high-temperature constant-temperature area and an H6 high-temperature constant-temperature area, and the silanization Y-port tee 302 is positioned
The outlet ends are respectively positioned in an H7 high-temperature constant-temperature area;
the temperature-changing control zone is specifically a temperature-changing control zone from T1 to T4;
the dehydration module 201 is located in the temperature swing control zone of T1,
the capture module 202 is located within the temperature swing control zone T2,
the focusing module 301 is located within the temperature swing control zone of T3,
the chromatographic column A401, the chromatographic column B402 and the heat exchanger 403 are all positioned in a temperature-changing control area of T4.
Further optimization, the dehydration module 201 is a polytetrafluoroethylene hollow pipe with the inner diameter of 2-4 mm and the length of 20-40 cm; the capture module 202 is filled with a quartz liner tube using graphitized carbon black and carbon molecular sieve composite filler as an adsorbent. Under the conditions of specified sampling flow rate, low temperature, sampling time range and the like, the adsorption behavior of the target object in the trapping module 202 meets a chromatographic rate equation, no penetration exists, and the trapping efficiency is about 100%.
Wherein H1-H7 are high temperature constant temperature areas, are electrically heated and are controlled by PID temperature; T1-T3 is a temperature-changing control area, which is refrigerated and electrically heated by a semiconductor element, and PID controls the temperature. T4 is a temperature-changing control area, and the heat exchanger 403 is arranged in a chromatographic column incubator; the condenser 404 drives the refrigerant, the refrigerant is evaporated and refrigerated in the heat exchanger 403, the refrigerant is heated by the heater in the column oven, and the PID temperature is controlled to 0-5 ℃ as the initial temperature of the chromatogram.
The chromatographic column A401 can be DB-10.25 um, 60m or DB6240.25um, 60 m;
column B402 can be PLOT-Q0.32 um, 30m or GasPLOT 0.32um, 30 m.
The detectors 501, 502 may be chromatographic detectors such as hydrogen flame ionization detectors FID, photo ionization detectors PID or mass spectrometry MS.
The embodiment discloses an automatic analysis method for atmospheric volatile organic compounds by low-temperature double-column chromatography, which comprises the following steps:
s1: the system is standby and ready to finish various preparation works before sampling: the method comprises the following steps of (1) controlling the temperature and the gas pressure of each temperature control module;
s2: collecting gas samples, and collecting different types of gas samples including diluted standard gas, internal standard gas, blank nitrogen and actual sample gas according to set flow rate, volume and different sample channels; and the collected gas sample is dehydrated at low temperature (-45 to-25 ℃) and adsorbed and trapped at low temperature (-45 to-2 ℃);
s3: dry blowing recovery, namely blowing the dehydration module to recover a target object into the capture module by using nitrogen at normal temperature (2-20 ℃), and purifying the capture module to remove carbon dioxide or other interfering substances;
s4: resolving and focusing, wherein the temperature of the trapping module is raised to 250-320 ℃, the target object is resolved and carried into a cold trap (-30 to-10 ℃) of the focusing module 301 by carrier gas for secondary concentration and purification;
S5: injecting a sample from a Y port, rapidly heating a cold trap of the focusing module 301 to 120-200 ℃ for analysis, and respectively entering the whole volume into two chromatographic columns A401 and B402 with different polarities in an equivalent manner according to pressure balance;
s6: hot cleaning, a hot cleaning flow path system, a hot cleaning dehydration module 201 and a trapping module 202;
s7: and (3) performing low-temperature chromatographic separation detection, namely performing chromatographic separation treatment in a low-temperature (0-5 ℃) chromatographic column incubator, detecting a separated target object, and analyzing and treating a result.
It should be noted that, in the attached drawings:
in fig. 4, abscissa: time (min), ordinate: chromatographic response (pA);
in fig. 5, abscissa: time (min), ordinate: chromatographic response (pA);
in fig. 6, abscissa: concentration (ppb), ordinate: response peak area (A);
in fig. 7, abscissa: time (min), ordinate: SIM ion strength.
To facilitate a further understanding of the invention by those skilled in the art, the invention is further described below in connection with specific embodiments.
Case one
SA1, system standby ready:
various preparation works before sampling are completed: h1, H2 and H7 are controlled to be at 150 ℃, H3-H6 are controlled to be at 100 ℃, the temperatures of the dehydration module 201 and the trapping module 202 are controlled to be at-30 ℃, the valve 102 is switched to the A state, and the rest parts are in default states.
SA2, gas sample collection:
according to the type, flow rate and volume of the gas to be collected, switching a selector valve 101 to a specified position to switch on an interface, starting a sampling pump 105, limiting the collection flow rate by a mass flowmeter 104, and closing the mass flowmeter 104 after reaching a specified sampling volume; and different sample channels are sequentially switched, and standard gas, internal standard gas, blank nitrogen, actual sample gas and the like are diluted for adsorption and trapping treatment.
SA3, dry blow recovery:
the temperature of the dehydration module 201T 1 is raised to 2 ℃, a selection valve 101 is arranged to an interface S5, a nitrogen mass flow meter 108 is 30ml/min, the dehydration module 2015 min is purged by nitrogen, the target is recovered to the capture module 202, and the adsorption tube is purified to remove interfering substances such as carbon dioxide.
SA4, resolving focus:
starting the low-temperature column temperature box T4 for refrigeration, circulating a refrigerant in the heat exchanger 403 and the condenser 404 by the compressor, and maintaining the low-temperature column temperature box at 5 ℃; the temperature of the focusing module 301 is reduced to-30 ℃, the valve 102 is switched to the B state, the trapping module 202 is communicated with the focusing module 301 at the moment, the trapping module 202 is heated to 300 ℃ to analyze a target object, and the target object is brought into the focusing module 301 by carrier gas (250 kPa, non-diversion mode) for secondary concentration and purification;
SA5, sample injection at Y port:
the focusing module 301 is heated up to 200 ℃ rapidly for analysis, and in the silanization Y-port tee 302, the whole volume of the mixture enters two chromatographic columns with different polarities, namely a chromatographic column A401 and a chromatographic column B402 respectively according to the pressure balance and the equal quantity to start chromatographic separation;
SA6, hot washing:
and (3) simultaneously carrying out sample introduction, switching the valve 102 to the A state, controlling the temperature of the dehydration module 201 and the temperature of the trapping module 202 to 200 ℃ and 320 ℃, respectively, selecting the valve to S2, sequentially opening the electromagnetic valve 106 and the nitrogen mass flow meter 108 to 50ml/min, and maintaining for 8 min. A hot cleaning flow path system, a hot cleaning dehydration module 201 and a capture module 202.
SA7, low temperature chromatography detection:
and (3) carrying out chromatographic separation in a low-temperature column incubator T4 at 5 ℃ for 15min, 5-75 ℃ at 8-200 ℃ for 5 min. The detector a501 and the detector B502 are respectively a hydrogen flame ionization detector FID, detect the separated target object, and analyze the result.
The separation effect is shown in fig. 4 and 5, and the partial target linearity is shown in fig. 5.
Case two
SC1, system standby ready:
various preparation works before sampling are completed: h1, H2 and H7 are controlled to be at 150 ℃, H3-H6 are controlled to be at 100 ℃, the temperatures of the dehydration module 201 and the trapping module 202 are respectively controlled to be-30 ℃ and-10 ℃, the valve 102 is switched to be in an A state, and the rest parts are in default states.
SC2, gas sample collection:
switching a selector valve 101 to a specified position to switch on an interface according to the type, flow rate and volume of gas to be collected, starting a sampling pump 105, limiting the collection flow rate by a mass flowmeter 104, and closing the mass flowmeter 104 after the specified sampling volume is reached; and different sample channels are sequentially switched, and standard gas, internal standard gas, blank nitrogen, actual sample gas and the like are diluted for adsorption and trapping treatment.
SC3, dry blow recovery:
heating the dehydration module 201T 1 to 2 ℃, setting a selection valve 101 to an interface S5, purging the dehydration module 2012 min by nitrogen with the nitrogen mass flow meter 108 of 20ml/min, recovering the target object to the capture module 202, and simultaneously purifying the adsorption tube to remove interfering substances such as carbon dioxide.
SC4, resolving focus:
the low-temperature column incubator T4 is started to refrigerate, and the compressor makes the refrigerant circulate in the heat exchanger 403 and the condenser 404, and the low-temperature column incubator at 10 ℃ is maintained. The temperature of the focusing module 301 is reduced to 10 ℃, the valve 102 is switched to the B state, the trapping module 202 is communicated with the focusing module 301 at the moment, the trapping module 202 is heated to 300 ℃ to analyze the target object, and the target object is brought into the focusing module 301 for secondary concentration and purification by carrier gas (1 ml/min, 8:1 diversion);
SC5, sample injection at Y port:
the focusing module 301 is heated up to 200 ℃ rapidly for analysis, and in the silanization Y-port tee 302, the whole volume of the mixture enters two chromatographic columns with different polarities, namely a chromatographic column A401 and a chromatographic column B402 respectively according to the pressure balance and the equal quantity to start chromatographic separation;
SC6, hot wash:
and (3) simultaneously carrying out sample introduction, switching the valve 102 to the A state, controlling the temperature of the dehydration module 201 and the temperature of the trapping module 202 to 200 ℃ and 320 ℃, respectively, selecting the valve to S2, sequentially opening the electromagnetic valve 106 and the nitrogen mass flow meter 108 to 50ml/min, and maintaining for 8 min. A hot cleaning flow path system, a hot cleaning dehydration module 201 and a capture module 202.
SC7, low temperature chromatography detection:
and (3) carrying out chromatographic separation in a low-temperature column incubator T4 at 5 ℃ for 15min, 5-75 ℃ at 8-200 ℃ for 5 min. The volatile organic compounds C2 and C3 are detected by a PLOT-Q chromatographic column connected with a detector B502 hydrogen flame ionization detector FID; the rest part is detected by a DB-1 chromatographic column connected with a detector A501 mass spectrum detector MS, and the result is analyzed and processed.
The atmospheric volatile organic compounds are sequentially controlled to be dehydrated and trapped at low temperature, under the given condition, the adsorption behavior of the target object in the trapping module meets a chromatographic rate equation, no penetration exists, and the trapping efficiency is about 100%. And after secondary concentration by a cold trap of the low-temperature chromatographic column, the whole volume is injected into a low-temperature chromatographic column warm box through a Y port, target substances of C2-C12 are separated by two chromatographic columns with different polarities, and qualitative and quantitative analysis is carried out by an FID or MS detector. The method effectively solves the problems that the chromatographic drift cannot be accurately determined and the like, has the advantages of compact structure, small device, simple operation and reliable result, and is beneficial to practical application and popularization.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the invention.
The present invention should be considered as limited only by the preferred embodiments and not by the specific details, but rather as limited only by the accompanying drawings, and as used herein, is intended to cover all modifications, equivalents and improvements falling within the spirit and scope of the invention.
Claims (10)
1. The utility model provides an atmosphere volatile organic compounds low temperature double column chromatography automatic analysis system which characterized in that: the device comprises a signal acquisition processing control unit, a sampling unit, a concentration and purification unit, a sample introduction unit, a low-temperature chromatographic separation unit and a detection unit, wherein the sampling unit, the concentration and purification unit, the sample introduction unit, the low-temperature chromatographic separation unit and the detection unit are connected with the signal acquisition processing control unit;
the sampling unit is used for selecting and collecting different types of gas samples, collecting diluted standard gas, internal standard gas, blank nitrogen and actual sample gas according to requirements, and providing a dry blowing gas source;
the concentration purification unit is used for carrying out purification treatment of dewatering, capturing and removing carbon dioxide interference on the collected gas;
The sample injection unit is used for respectively feeding the target object subjected to thermal analysis into chromatographic columns with different polarities in a whole volume in an equivalent manner according to pressure balance;
the low-temperature chromatographic separation unit is used for focusing the target object at low temperature and controlling the temperature programming at the same time so that the target object flows into the detection unit one by one;
the detection unit is used for receiving and amplifying a target object signal to form a chromatogram so as to perform qualitative and quantitative analysis;
and the signal acquisition processing control unit is connected with each unit and is used for acquiring, processing or reversely controlling the temperature, the pressure and the analog signals of each unit.
2. The atmospheric volatile organic compound low-temperature dual-column chromatography automatic analysis system of claim 1, characterized in that: the concentration and purification unit comprises a dehydration module and a trapping module which are connected with the sample introduction unit.
3. The atmospheric volatile organic compound low-temperature dual-column chromatography automatic analysis system according to claim 2, characterized in that: the sample introduction unit comprises a focusing module, a silanization Y-port tee joint and an electronic pressure controller EPC, one end of the focusing module is connected with the sample introduction unit, the other end of the focusing module is connected with the low-temperature chromatographic separation unit through the silanization Y-port tee joint, and the electronic pressure controller EPC is connected with the sample introduction unit.
4. The atmospheric volatile organic compound low-temperature dual-column chromatography automatic analysis system according to claim 3, characterized in that: the low-temperature chromatographic separation unit comprises a chromatographic column A, a chromatographic column B, a heat exchanger and a condenser, wherein one end of the chromatographic column A and one end of the chromatographic column B are respectively connected with two outlets of the silanization Y-port tee joint, the other end of the chromatographic column A and the other end of the chromatographic column B are connected with the detection unit, and the heat exchanger and the condenser form a refrigeration cycle mechanism.
5. The system of claim 4, wherein the system comprises: the detection unit comprises a detector A and a detector B, and the detector A and the detector B are respectively communicated with the chromatographic column A and the chromatographic column B.
6. The system of claim 5, wherein the system comprises: the sampling unit comprises an eight-in one-out selector valve, an eight-way switching valve, a silanization three-way valve, a sampling flowmeter, a sampling pump, a three-way electromagnetic valve, a pressure sensor and a nitrogen sampling flowmeter;
the eight-in one-out selector valve has S0 bit and S1-8 bit; the S1 bit is dead block, the S2 bit is a blowback discharge port, the S3 bit is standard gas 2, the S4 bit is standard gas 1, the S5 bit is blank nitrogen, the S6 bit is internal standard gas, the S7 bit is sample gas, and the S8 bit is dead block;
The eight-way switching valve is provided with a P1-P8 position, a P1 position is connected with an S0 position of the eight-in one-out selector valve, a P2 position is connected with an inlet of the dehydration module, a P3 position is connected with an inlet of the trapping module, a P4 position is connected with an inlet of the focusing module, a P5 position is connected with the EPC, a P6 position is connected with an outlet of the trapping module, a P7 position is connected with the silanization tee joint, and a P8 position is connected with an outlet of the dehydration module;
the nitrogen sampling flowmeter is used for being connected with a nitrogen source, the nitrogen sampling flowmeter is connected with the three-way electromagnetic valve, and two outlets of the three-way electromagnetic valve are respectively communicated with the S5 position and the inlet of the silanization three-way valve; a pressure sensor is arranged between the nitrogen sampling flowmeter and the three-way electromagnetic valve;
the sampling pump is connected with the silanization tee joint, a sampling flow meter is arranged between the sampling pump and the silanization tee joint, and the end part of the sampling pump is an emptying end.
7. The system of claim 5, wherein the system comprises: the signal acquisition processing control unit comprises temperature and pressure sensors, PID control loops of each temperature control area, and a high-temperature constant-temperature area and a variable-temperature control area which are formed;
the high-temperature constant-temperature area is specifically H1-H7,
wherein:
the eight-in one-out selector valve, the eight-way switching valve, the silanization three-way valve and the silanization Y-port three-way valve are positioned in an H1 high-temperature constant-temperature area, an S4-7 inlet end is positioned in an H2 high-temperature constant-temperature area, two ends of the dehydration module are respectively provided with an H3 high-temperature constant-temperature area and an H4 high-temperature constant-temperature area, two ends of the trapping module are respectively provided with an H5 high-temperature constant-temperature area and an H6 high-temperature constant-temperature area, and two ends of the silanization Y-port three-way valve are positioned in an H5 high-temperature constant-temperature area and an H6 high-temperature constant-temperature area
The outlet ends are respectively positioned in an H7 high-temperature constant-temperature area;
the temperature-changing control zone is a temperature-changing control zone T1-T4;
the dehydration module is positioned in a temperature-changing control zone of T1,
the trapping module is positioned in the temperature-changing control zone of T2,
the focusing module is located in the temperature-changing control zone of T3,
the chromatographic column A, the chromatographic column B and the heat exchanger are all positioned in a temperature-changing control area of T4.
8. The system of claim 6, wherein the system comprises: the dehydration module is a polytetrafluoroethylene hollow pipe with the inner diameter of 2-4 mm and the length of 20-40 cm; the capture module 202 is filled with a quartz liner tube using graphitized carbon black and carbon molecular sieve composite filler as an adsorbent.
9. The system according to claim 7, wherein the system comprises: H1-H7 are high temperature constant temperature areas, are electrically heated and are controlled by PID; T1-T3 are temperature change control areas, which are refrigerated and electrically heated by semiconductor elements, and controlled by PID;
t4 is a temperature-changing control area, and the heat exchanger is arranged in a chromatographic column temperature box; the refrigerant is driven by a condenser compressor, is evaporated and refrigerated in a heat exchanger, is heated by a heater in a column oven, and the PID temperature is controlled to 0-5 ℃ as the initial temperature of the chromatogram.
10. An automatic analysis method of low-temperature double-column chromatography of atmospheric volatile organic compounds, which is characterized by comprising the use of the automatic analysis system of low-temperature double-column chromatography of atmospheric volatile organic compounds in claim 9, and the specific method is as follows:
S1: the system is standby and ready to finish various preparation works before sampling: the method comprises the following steps of (1) controlling the temperature and the gas pressure of each temperature control module;
s2: collecting gas samples, and collecting different types of gas samples including diluted standard gas, internal standard gas, blank nitrogen and actual sample gas according to set flow rate, volume and different sample channels; and the collected gas sample is dehydrated at low temperature (-45 to-25 ℃) and adsorbed and trapped at low temperature (-45 to-2 ℃);
s3: dry blowing recovery, namely blowing the dehydration module to recover a target object into the capture module by using nitrogen at normal temperature (2-20 ℃), and purifying the capture module to remove carbon dioxide or other interfering substances;
s4: resolving and focusing, wherein the temperature of the trapping module is raised to 250-320 ℃, the target object is resolved and carried into a cold trap (-30 to-10 ℃) of the focusing module 301 by carrier gas for secondary concentration and purification;
s5: injecting a sample from a Y port, rapidly heating a cold trap of a focusing module to 120-200 ℃ for analysis, and respectively feeding the whole volume into two chromatographic columns A and B with different polarities in an equivalent manner according to pressure balance;
s6: the system comprises a heat cleaning device, a heat cleaning flow path system, a heat cleaning dehydration module and a trapping module;
s7: and (3) performing low-temperature chromatographic separation detection, namely performing chromatographic separation treatment in a low-temperature (0-5 ℃) chromatographic column incubator, detecting a separated target object, and analyzing and treating a result.
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| CN114755349B (en) | 2022-09-02 |
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