CN115343381A - Detection device and method for volatile organic compounds in waste gas of fixed pollution source - Google Patents

Detection device and method for volatile organic compounds in waste gas of fixed pollution source Download PDF

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CN115343381A
CN115343381A CN202210808164.1A CN202210808164A CN115343381A CN 115343381 A CN115343381 A CN 115343381A CN 202210808164 A CN202210808164 A CN 202210808164A CN 115343381 A CN115343381 A CN 115343381A
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李美玲
林鸿
臧金亮
李源清
张晓东
胡娜
翟仲溪
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Zhengzhou Institute Of Advanced Measurement Technology
National Institute of Metrology
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Abstract

The invention discloses a detection device and a detection method for volatile organic compounds in fixed pollution source waste gas, wherein a bottle cap can be opened to clean a vacuum bottle after the vacuum bottle is polluted, so that the detection device is convenient, quick and cost-saving, can perform long-time sampling, and is a reasonable sampling device worthy of selection. Meanwhile, the invention can detect 117 VOCs, adds an effective detection scheme for the fixed pollution source waste gas with various pollutants, high concentration and difficult detection, has great significance for perfecting a monitoring system, strengthening environmental management, ensuring human health and standardizing the determination method of volatile organic compounds in the fixed pollution source waste gas, and simultaneously reduces potential safety hazards for enterprises and realizes resource saving.

Description

Detection device and method for volatile organic compounds in waste gas of fixed pollution source
Technical Field
The invention relates to the field of volatile organic compound detection, in particular to a detection device and a detection method for volatile organic compounds in fixed pollution source waste gas.
Background
Volatile organic compounds have a number of levels of definition, which the World Health Organization (WHO) defines as: organic compounds having a melting point below room temperature and a boiling point below 200-260 ℃ under normal atmospheric pressure are collectively referred to. VOCs have photochemical activity, can cause photochemical smog to influence the respiratory tract function of people under certain conditions, cause symptoms of chest distress, nausea, fatigue and the like, and contain a plurality of toxic, harmful, inflammable and explosive gases which cause various uncomfortable reactions of human bodies, such as irritation to skin and mucous membranes, anesthesia action on the central nervous system and even carcinogenesis. VOCs are important precursors of Secondary Organic Aerosols (SOA), can form haze pollution and are also near-ground O 3 The photochemical reaction of the VOC-NOx, an important precursor formed, increases the ozone concentration in the atmospheric troposphere, causing a greenhouse effect.
The data quality is the core of emission reduction, and accurate detection of VOCs is the requirement of current environmental protection work. However, the existing method for detecting volatile organic compounds in waste gas of a fixed pollution source is still not complete enough, and the types of the volatile organic compounds are few.
The collection and pre-treatment of the sample is critical throughout the analysis process. If the collected sample can not truly reflect the total body of the measured object or the components to be measured are greatly lost in the pretreatment process, an accurate analysis result can not be obtained.
The sampling of gaseous pollutants is generally divided into a direct sampling method and a concentration sampling method, and the vacuum bottle sampling specified in the sample collection method listed in the industry standard HJ/T397-2007 belongs to the direct sampling method. At present, the vacuum bottle technology is more and more mature, not only can collect large-volume samples, but also has relatively mature quality control measures for leak detection and cleaning of a sampling container, and compared with other sampling, the vacuum bottle is convenient to operate, has no discrimination effect on target compounds during sample collection, and can collect all-component samples. In addition to sample collection, the emphasis of detection techniques for VOCs is also on pretreatment of the sample. The pretreatment methods adopted by the VOCs are different according to the state of the sample, the pretreatment is complex, and the influence on the analysis result is large.
The existing standard related to the monitoring of the volatile organic compounds in the waste gas of the fixed pollution source has a plurality of loopholes. The determination target in environmental standard "solid phase adsorption-thermal desorption/gas chromatography-mass spectrometry for determining volatile organic compounds in exhaust gas of fixed pollution sources" (HJ 734-2014) is a characteristic species in the electronic industry, does not comprise characteristic emission factors and components specified by emission standards in most industries, and cannot represent the actual situation of VOCs in an exhaust funnel. In the environmental standard gas chromatography-mass spectrometry for determining VOCs (volatile organic compounds) in waste gas of stationary pollution sources (DB 50/T679-2016), an inerted stainless steel tank is specified for sampling, and the inert stainless steel tank is concentrated by a gas cold trap concentrator and then enters a gas chromatography-mass spectrometry combination instrument for analysis. The sampling tank is difficult to clean after collecting high-concentration waste gas, and the cost of the sampling tank is very high, so that the sampling tank is used for collecting waste gas of a fixed pollution source and needs very high cost. Similarly, fixing too high a concentration of volatile organic compounds in the source of contamination, if not diluted, can easily result in contamination of the instrument and delay normal detection procedures. The device for sampling in the air bag method for sampling volatile organic compounds in waste gas of fixed pollution sources (HJ 732-2014) in the environmental standard is an air bag, and only instantaneous samples can be acquired, so that long-time sampling is difficult to realize. In addition, the existing standards have few discharge factors of VOCs (volatile organic compounds) which are main characteristics of the discharge industry of VOCs, and cannot meet the requirement of environmental supervision.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a detection device and a detection method for fixing volatile organic compounds in pollution source waste gas.
In order to achieve the purpose, the invention adopts the following technical scheme:
a detection device for volatile organic compounds in fixed pollution source waste gas comprises a vacuum bottle, a quantitative loop sample introduction device, a gas cold trap concentrator, a gas chromatography-mass spectrometer and a data processing system which are sequentially connected; the vacuum bottle is used for collecting the waste gas of the fixed pollution source, the quantitative ring sampling device is used for performing quantitative ring collection on the waste gas of the fixed pollution source in the vacuum bottle and sampling the waste gas to a third-stage cold trap of the gas cold trap concentrator for focusing, and the gas cold trap concentrator sweeps the focused waste gas of the fixed pollution source into the gas chromatography-mass spectrometer by using carrier gas; the gas chromatography-mass spectrometer is used for carrying out gas chromatography separation on the waste gas of the fixed pollution source, wherein a hydrogen flame ionization detector is used for detecting C2-C3 target compounds, a mass spectrometer is used for detecting the rest target compounds, and detection data are sent to a data processing system for data analysis.
Further, the volatile organic compounds include 117 species, including the volatile organic compounds in 57 PAMS standard gases, 13 aldehyde ketone compounds, and the volatile organic compounds in 47 TO-15 standard gases.
Still further, the volatile organic includes acetylene, ethylene, propylene, n-butene, butadiene, trans-2-butene, cis-2-butene, 1-pentene, 2-methyl-1,3-butadiene, trans-2-pentene, cis-2-pentene, 1-hexene, ethane, propane, isobutane, n-butane, isopentane, n-pentane, 2,2-dimethylbutane, cyclopentane, 2,3-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexane, methylcyclopentane, 2,4-dimethylpentane, cyclohexane, 2-methylhexane, 2,3-dimethylpentane, 3-methylhexane, 5657 zxft 57 trimethylpentane, n-heptane, methylcyclohexane, 2,3,4-trimethylpentane, 2-methylheptane, 3-methylheptane, n-octane, n-nonane, 5639-undecane, dodecane, benzene, toluene, m-heptane, p-xylene, styrene, o-xylene, cumene, benzaldehyde, n-propylbenzene, 1-ethyl-3-methylbenzene, 1-ethyl-4-methylbenzene, 1,3,5-trimethylbenzene, 1-ethyl-2-methylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, 1,4-diethylbenzene, 1,3-diethylbenzene, naphthalene, acetaldehyde, acrolein, acetone, propionaldehyde, isopropanol, methacrolein, methyl tert-butyl ether, vinyl acetate, n-butyraldehyde, 2-butanone, ethyl acetate, tetrahydrofuran, crotonaldehyde, valeraldehyde, 1,4-dioxane, methyl methacrylate, 4-methyl-2-pentanone, 2-hexanone, hexanal, m-tolualdehyde, formaldehyde, difluorodichloromethane, methyl chloride, 1,1,2,2-tetrafluoro-1,2-dichloroethane, vinyl chloride, monobromomethane, ethyl chloride, fluorotrichloromethane, 1,1-dichloroethylene, dichloromethane, 1,2,2-trifluoro-1,1,2-trichloroethane, trans-1,2-dichloroethylene, 1,1-dichloroethane, cis 1,2-dichloroethylene, trichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloromethane, and mixtures thereof carbon tetrachloride, 1,2-dichloropropane, bromodichloromethane, trichloroethylene, trans-1,3-dichloro-1-propene, cis-1,3-dichloropropene, 1,1,2-trichloroethane, dibromomonochloromethane, 1,2-dibromoethane, tetrachloroethylene, chlorobenzene, tribromomethane, 1,1,2,2-tetrachloroethane, chlorotoluene, 1,3-dichlorobenzene, p-dichlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,1,2,3,4,4-hexachloro-1,3-butadiene, carbon disulfide.
Furthermore, the quantitative loop sample introduction device has the functions of automatic quantitative sampling and automatic internal standard addition, and can realize automatic sample introduction of samples in the vacuum bottle.
Furthermore, the gas cold trap concentrator has the functions of automatic quantitative sampling, automatic addition of standard used gas and automatic addition of internal standard used gas, and has a three-stage cold trap, wherein the third-stage cold trap can be cooled to-190 ℃.
Furthermore, in the gas chromatography-mass spectrometer, the gas chromatograph can perform electronic pressure control on the carrier gas, and the column oven has a temperature programming function; the mass spectrometer has a 70eV electron bombardment ion source, and has the functions of NIST mass spectrum gallery, manual/automatic tuning, data acquisition, quantitative analysis and spectral gallery retrieval.
The invention also provides a method for utilizing the detection device, which comprises the following specific processes:
s1, cleaning a vacuum bottle by using a vacuum bottle cleaning device, collecting a fixed pollution source waste gas sample by using one cleaned vacuum bottle, and collecting a bottle of internal standard use gas by using the other cleaned vacuum bottle;
s2, collecting a fixed pollution source waste gas sample collected in a vacuum bottle through a sample quantitative ring in a quantitative ring sampling device, collecting corresponding internal standard use gas through an internal standard quantitative ring in the quantitative ring sampling device, and focusing through a third-stage cold trap of a gas cold trap concentrator;
s3, blowing the mixture into a gas chromatography-mass spectrometer for separation by using carrier gas, detecting C2-C3 target compounds by using a hydrogen flame ionization detector, detecting the rest target compounds by using a mass spectrometer, and analyzing sample data by using a data processing system; C2-C3 target compounds are qualitative by retention time and quantitative by an external standard method; comparing the retention time and mass spectrogram of other target compounds with standard substances for qualitative determination, and quantifying by using an internal standard method.
Further, in step S2, the quantitative loop sample injection device has 10 inlet and outlet positions, and the number 1 position, the number 2 position, the number 3 position, the number 4 position, the number 5 position, the number 6 position, the number 7 position, the number 8 position, the number 9 position and the number 10 position are sequentially arranged in a circle at equal intervals; the operation modes of the quantitative loop sampling device and the gas cold trap concentrator are divided into two modes, namely a sampling mode and a sampling mode;
in a sampling mode, a sample flows in through the No. 1 position, flows into the sample quantitative ring through the No. 2 position, fills the sample quantitative ring and discharges redundant samples through the No. 6 position and the No. 5 position in sequence; the internal standard enters from the No. 4 position by using gas, flows into the internal standard quantitative ring through the No. 3 position, fills the internal standard quantitative ring and discharges redundant gas through the No. 9 position and the No. 10 position in sequence; carrier gas enters from the No. 8 position and enters a third-stage cold trap of the gas cold trap concentrator through the No. 7 position for focusing;
in a sample introduction mode, a sample enters from the No. 1 position and enters the sample quantitative ring through the No. 2 position, and meanwhile, redundant samples are discharged through the No. 10 position; injecting the internal standard from the No. 4 position by using gas, and discharging redundant gas from the No. 5 position; and carrier gas enters through the No. 8 position, enters the internal standard quantitative ring through the No. 9 position, pushes the internal standard gas to sequentially enter the No. 3 position and the No. 2 position, then enters the sample quantitative ring, pushes the sample to sequentially enter the No. 6 position and the No. 7 position, and finally enters the third-stage cold trap of the gas cold trap concentrator for focusing.
Further, the specific drawing process of the standard curve required by the data processing system for analysis is as follows: according to the sample introduction process of the waste gas sample of the fixed pollution source, 1mL of standard use gas is respectively extracted from 0.10 mu mol/mol, 0.40 mu mol/mol, 0.80 mu mol/mol, 1.2 mu mol/mol and 2.00 mu mol/mol to enter a quantification ring of a quantification ring sample introduction device, 0.25mL of 1.00 mu mol/mol internal standard use gas is correspondingly extracted, the internal standard use gas enters a gas chromatography-mass spectrometer for measurement after being focused by a third-stage cold trap of a gas cold trap concentrator, and a data processing system is used for drawing a standard curve;
sequentially measuring from low concentration to high concentration according to instrument reference conditions;
drawing a standard curve by taking the concentration of the C2-C3 target compound as an abscissa and the response value of a chromatographic peak as an ordinate;
drawing a standard curve by adopting an average relative response factor method for the rest target compounds, calculating relative response factors according to a formula (1), and calculating average relative response factors of all standard concentration points of the target compounds according to a formula (2);
Figure BDA0003739165040000071
in the formula: RRF i Representing the relative response factor of the target compound at the i point in the standard series; a. The i Representing the response value of the quantitative ion of the target compound at the ith point in the standard series; a. The ISi Expressing the response value of the standard ion in the ith point in the standard series; rho IS Represents the mole fraction of the internal standard in the standard series, nmol/mol; rho i Represents the mol fraction of the target compound at the i-th point in the standard series, nmol/mol;
average relative response factor of target compound
Figure BDA0003739165040000072
The calculation is performed according to equation (2):
Figure BDA0003739165040000073
in the formula:
Figure BDA0003739165040000074
represents the average relative response factor of the target compound; RRF i Representing the ith point object in the standard series relative response factor of the compound; n represents a standard series of points;
the standard curve requires that the relative standard deviation of the relative response factors should be equal to or less than 30%, or a linear standard curve established by the least square method, the correlation coefficient of which needs to be equal to or greater than 0.990.
Further, in step S3, the quantification of the C2-C3 target compound is quantified by external standard method, and calculated according to formula (5):
Figure BDA0003739165040000075
in the formula: rho x Represents the concentration of the target compound in the sample,. Mu.g/m 3 ；ρ a Represents the molar fraction of the target compound obtained from the standard curve, nmol/mol; m represents the molar mass of the target compound, g/mol;22.4 represents the molar volume of the gas in the standard state, L/mol; f represents the dilution factor;
the quantification of the remaining target compounds was quantified by internal standard method, and calculated according to formula (6):
Figure BDA0003739165040000081
in the formula: rho x Represents the concentration of the target compound in the sample,. Mu.g/m 3; a. The X Representing a response value of the target compound quantification ion; a. The IS Expressing the response value of the ion quantified by the internal standard substance; rho IS Represents the mole fraction of the internal standard in the sample, nmol/mol;
Figure BDA0003739165040000082
represents the average relative response factor of the target compound; m represents the molar mass of the target compound, g/mol;22.4 tableIndicating the molar volume of the gas in a standard state, L/mol; f represents the dilution factor.
The invention has the beneficial effects that:
the invention provides a device and a method for detecting 117 volatile organic compounds in fixed pollution source waste gas in a vacuum bottle sampling quantitative loop sampling mode. Meanwhile, the invention can detect 117 VOCs, adds an effective detection scheme for the fixed pollution source waste gas with various pollutants, high concentration and difficult detection, has great significance for perfecting a monitoring system, strengthening environmental management, ensuring human health and standardizing the determination method of volatile organic compounds in the fixed pollution source waste gas, and simultaneously reduces potential safety hazards for enterprises and realizes resource saving.
The method is suitable for gas chromatography-mass spectrometry for fixing 117 volatile organic compounds in the pollutant source organized and unorganized emission waste gas. The 117 volatile organic compounds include volatile organic compounds in 57 PAMS standard gases, 13 aldehyde ketone compounds and volatile organic compounds in 47 TO-15 standard gases, and basically include main characteristic VOCs emission factors of various VOCs emission industries.
Drawings
FIG. 1 is a schematic view showing the connection of an apparatus in example 1 of the present invention;
FIG. 2 is a schematic diagram of the quantitative loop sampling device according to embodiment 2 of the present invention operating in a sampling mode;
FIG. 3 is a schematic view of the operation of the quantitative loop sampling device in embodiment 2 of the present invention in a sampling mode;
FIG. 4 is a GC-FID chromatogram of 5C 2-C3 target compounds at a concentration point of 2ppm in example 2 according to the invention;
FIG. 5 is a GC-MS total ion flow graph of the 112 remaining target compounds at the 2ppm concentration point in example 2 of the invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
Example 1
The embodiment provides a detection device for volatile organic compounds in fixed pollution source waste gas, as shown in fig. 1, the detection device comprises a vacuum bottle 1, a quantitative loop sample introduction device 2, a gas cold trap concentrator 3, a gas chromatography-mass spectrometer 4 and a data processing system 5 which are connected in sequence; the vacuum bottle 1 is used for collecting the waste gas of the fixed pollution source, the quantitative loop sampling device 2 is used for performing quantitative loop collection on the waste gas of the fixed pollution source in the vacuum bottle 1 and feeding the waste gas into a third-stage cold trap of the gas cold trap concentrator 3 for focusing, and the gas cold trap concentrator sweeps the focused waste gas of the fixed pollution source into the gas chromatography-mass spectrometer 4 by using carrier gas; the gas chromatography-mass spectrometer 4 is used for carrying out gas chromatography separation on waste gas of a fixed pollution source, wherein a hydrogen flame ionization detector is used for detecting 5C 2-C3 target compounds (acetylene, ethylene, ethane, propylene and propane), a mass spectrometer is used for detecting the rest target compounds, and detection data are sent to a data processing system for data analysis.
In this embodiment, there are 117 target volatile organic compounds TO be detected by the above detection device, as shown in table 1, including volatile organic compounds in 57 PAMS standard gases, volatile organic compounds in 13 aldehyde ketone compounds and volatile organic compounds in 47 TO-15 standard gases.
TABLE 1 Standard gas mixture of 117 volatile organic compounds
Figure BDA0003739165040000101
Figure BDA0003739165040000111
In this embodiment, the vacuum flask 1 is a glass sampling tank with a deactivated inner wall, and has a volume of 1L and a pressure resistance value of > 150kPa. This example uses an Entech Bottle-Vac TM 1L sampling Bottle.
In this embodiment, the vacuum bottle 1 is cleaned using a vacuum bottle cleaning device that can pump the vacuum bottle to vacuum (< 10 Pa). Preferably, the vacuum bottle cleaning device has the functions of heating, humidifying and pressurizing cleaning. The embodiment adopts an Entech3108D full-automatic can cleaning instrument. The tank cleaning instrument is an independent instrument for cleaning the vacuum bottle.
It should be noted that the quantitative loop sampling device 2 has functions of automatic quantitative sampling and automatic internal standard addition, and can realize automatic sample introduction of samples in a vacuum bottle. This example used an Entech7650-M auto headspace sampler.
In this example, the standard gas and the sample share the same sample quantification loop, and the standard gas is 1cc quantification loop, and the standard gas is 0.25cc quantification loop. The size of the quantification loop determines the maximum sample size of the sample. This example used an Entech 1cc quantitation loop and an Entech 0.25cc quantitation loop.
In this embodiment, the gas cold trap concentrator has functions of automatic quantitative sampling, automatic addition of standard use gas and automatic addition of internal standard use gas, and has three stages of cold traps (the third stage of cold traps can be cooled to-190 ℃). The connecting pipelines of the gas cold trap concentrator and the gas chromatography-mass spectrometer are made of inert materials. This example uses an Entech 7200 atmospheric preconcentrator.
In the present embodiment, in the gas chromatograph-mass spectrometer, the gas chromatograph can perform electron pressure control on the carrier gas, and the column oven has a temperature programming function; the mass spectrometer has a 70eV Electron Impact (EI) ion source, and has the functions of NIST mass spectrum gallery, manual/automatic tuning, data acquisition, quantitative analysis, spectral gallery retrieval and the like. This example uses an Agilent 8890/5977B GC-MS.
In the gas chromatography-mass spectrometer, the specification of a chromatographic column for GC-FID analysis of the C2-C3 target compound is a quartz capillary chromatographic column, the size of the chromatographic column is 30m multiplied by 320 mu m multiplied by 0.2 mu m, and the stationary phase is styrene-divinylbenzene or other equivalent capillary chromatographic columns. An Agilent HP-PLOT/Q + PT column (30 m.times.320. Mu.m.times.20 μm) was used in this example.
In the gas chromatography-mass spectrometer, the specification of a chromatographic column for GC-MS analysis of other target compounds is a quartz capillary chromatographic column, 60m is multiplied by 320 mu m is multiplied by 1 mu m, and the stationary phase is 100% dimethyl polysiloxane or other equivalent capillary chromatographic columns are used. In this example, agilent 122-1063DB-1 chromatography column (60 m. Times.250. Mu. M. Times.1 μm) was used.
In this embodiment, when preparing the standard curve series, the standard used gas needs to be diluted, and the dilution factor of the gas dilution device can reach at least 100 times. In this example, an ENTECH 4700 high-precision dilution instrument was used. The diluter is a stand-alone instrument for diluting a standard gas into a standard use gas.
In this example, the carrier gas is helium (purity ≧ 99.999%).
In this example, liquid nitrogen was used for cooling in the initial process of the M3 focusing process (7200M 3 focusing, focusing temperature: -190 ℃ C., temperature control by low temperature solenoid valve) and the temperature raising program of the GC-MS (5 ℃ C. For 6min, temperature control by low temperature solenoid valve) of the gas cold trap concentrator.
Example 2
The present embodiment provides a method using the apparatus of embodiment 1, which includes the following specific steps:
s1, cleaning a vacuum bottle by using a vacuum bottle cleaning device, collecting a 2.00 mu mol/mol fixed pollution source waste gas sample by using one cleaned vacuum bottle, and collecting a bottle of 1.00 mu mol/mol internal standard used gas by using the other cleaned vacuum bottle.
In this example, the internal standard used was 4-component internal standard gas with 1.00. Mu. Mol/mol gas, including bromochloromethane, 1,4-difluorobenzene, chlorobenzene-d 5, 4-bromofluorobenzene.
S2, collecting 1mL of the fixed pollution source waste gas sample collected in the vacuum bottle through a sample quantitative ring in a quantitative ring sampling device, collecting 0.25mL of corresponding internal standard use gas through an internal standard quantitative ring in the quantitative ring sampling device, and focusing through a third-stage cold trap of a gas cold trap concentrator.
In this embodiment, the quantitative loop sample injection device has 10 inlet and outlet positions, wherein the 1 st, 2 nd, 3 rd, 4 th, 5 th, 6 th, 7 th, 8 th, 9 th and 10 th positions are arranged in a circle at equal intervals; the operation mode of quantitative loop sampling device and gas cold trap concentrator divide into two kinds, sample mode and kind mode promptly, specifically do:
as shown in fig. 2, in the sampling mode, the sample flows in through the position No. 1, flows into the sample quantitative ring 21 through the position No. 2, fills the sample quantitative ring 21, and discharges the excessive sample through the positions No. 6 and No. 5 in sequence; the internal standard enters from the No. 4 position by using gas, flows into the internal standard quantitative ring 22 through the No. 3 position, fills the internal standard quantitative ring 22 and discharges redundant gas through the No. 9 position and the No. 10 position in sequence; the carrier gas enters from the No. 8 position and enters the third stage cold trap of the gas cold trap concentrator through the No. 7 position for focusing.
As shown in fig. 3, in the sample injection mode, the sample enters from the position 1 and enters the sample quantitative loop 21 through the position 2, and meanwhile, the redundant sample is discharged through the position 10; injecting the internal standard from the No. 4 position by using gas, and discharging redundant gas from the No. 5 position; and carrier gas enters through the No. 8 position, enters the internal standard quantification ring 22 through the No. 9 position, pushes the internal standard using gas to enter the No. 3 position and the No. 2 position in sequence, then enters the sample quantification ring, pushes the sample to enter the No. 6 position and the No. 7 position in sequence, and finally enters the third-stage cold trap of the gas cold trap concentrator for focusing.
In this embodiment, the operation parameters of the quantitative loop sample injection device (7650M) and the gas cold trap concentrator (7200) are as follows:
temperature: 7650M holder heater: 80 ℃;7650M transfer line heater between gripper and dosing ring module: 80 ℃; heater of 7650M transmission line between dosing ring module and 7200M 3: 100 ℃;7650M heater for dosing ring valve: 150 ℃; focusing was performed using 7200M3, focusing temperature: -190 ℃.
Duration: internal standard washing: 0.50min; quantitative ring wash delay: 0.10min; washing with a quantitative ring: 0.50min; the sample was passed through the quantification loop module to 7200M3 and focused: 3.00min; injection into a GC:1.00min; baking in a quantitative ring mode: 1.00min.
And S3, blowing the mixture into a gas chromatography-mass spectrometer for separation by using carrier gas, detecting the C2-C3 target compounds by using a hydrogen flame ionization detector, and detecting the rest target compounds by using a mass spectrometer. C2-C3 target compounds (5) are qualitative by retention time and quantitative by an external standard method; the remaining target compounds (112) were characterized by retention time and mass spectra versus standard and quantified by internal standard.
The GC-FID analysis C2-C3 target compound reference conditions are as follows:
temperature rising procedure: keeping the temperature at 5 ℃ for 6min, heating to 170 ℃ at the speed of 5 ℃/min, and keeping the temperature for 5min; then the temperature is raised to 200 ℃ at the speed of 15 ℃/min and kept for 10min. Flow rate of the chromatographic column: 1.0ml/min; sample inlet temperature: at 100 ℃.
Detector temperature: at 250 deg.c.
The GC-MS analysis reference conditions for the rest of the target compounds are as follows:
temperature rising procedure: keeping the temperature at 5 ℃ for 6min, heating to 170 ℃ at the speed of 5 ℃/min, and keeping the temperature for 5min; then the temperature is raised to 200 ℃ at the speed of 15 ℃/min and kept for 10min. Flow rate of the chromatographic column: 1.0ml/min; sample inlet temperature: at 100 ℃.
MS transmission line temperature: at 250 ℃ to obtain a mixture. Ion source temperature: 230 ℃ to 230 ℃. The scanning mode is as follows: EI (full scan). Solvent delay time: 8.50min. Scanning range: segmented scanning: 8.50min start, scan range: 25amu to 260amu. Ionization energy: 70eV.
In this embodiment, the specific process of plotting the standard curve is as follows: according to the sampling process of the waste gas sample of the fixed pollution source, 1mL of standard use gas is respectively extracted from 0.10 mu mol/mol, 0.40 mu mol/mol, 0.80 mu mol/mol, 1.2 mu mol/mol and 2.00 mu mol/mol to enter a quantitative ring of a quantitative ring sampling device, 0.25mL of 1.00 mu mol/mol internal standard use gas is correspondingly extracted, the internal standard use gas enters a gas chromatography-mass spectrometer for measurement after being focused by a third-stage cold trap of a gas cold trap concentrator, and a data processing system is used for drawing a standard curve. The measurement is carried out according to the reference conditions of the instrument from low concentration to high concentration in sequence (the standard curve at least comprises 5 concentration points, wherein 0 point is not contained, and the standard curve can be adjusted according to the actual sample condition). In this example, the standard gas used was a mixture of 117 volatile organic compounds, including 57 PAMS components, 13 aldone compounds and 47 TO-15 components.
And (4) drawing a standard curve by taking the concentration of the C2-C3 target compound as an abscissa and the response value of a chromatographic peak as an ordinate.
And drawing a standard curve by adopting an average relative response factor method for the rest target compounds, calculating relative response factors according to a formula (1), and calculating average relative response factors of all standard concentration points of the target compounds according to a formula (2).
Figure BDA0003739165040000161
In the formula: RRF i Representing the relative response factor of the target compound at the ith point in the standard series; a. The i Representing the response value of the quantitative ion of the target compound at the ith point in the standard series; a. The ISi Expressing the response value of the standard ion in the ith point in the standard series; rho IS Represents the mole fraction of the internal standard in the standard series, nmol/mol; rho i Represents the mole fraction, nmol/mol, of the target compound at point i in the standard series.
Average relative response factor of target compound
Figure BDA0003739165040000171
The calculation is performed according to equation (2):
Figure BDA0003739165040000172
in the formula:
Figure BDA0003739165040000173
represents the average relative response factor of the target compound; RPF i Representing the relative response factor of the target compound at the i point in the standard series; n represents the standard series of points.
The standard curve requires that the Relative Standard Deviation (RSD) of the relative response factor should be equal to or less than 30%, or a linear standard curve established by the least square method, the correlation coefficient of which needs to be equal to or greater than 0.990.
In this example, the target compound was characterized by the following methods:
the C2-C3 target compounds are characterized by relative retention times; the remaining target compounds are characterized by relative retention time, sample to standard mass spectra comparison.
In this example, the target compound was quantified by:
quantification of C2-C3 target Compounds was quantified by external standard method and calculated according to equation (5)
Figure BDA0003739165040000174
In the formula: rho x Represents the concentration of the target compound in the sample,. Mu.g/m 3; rho a Represents the molar fraction of the target compound obtained from the standard curve, nmol/mol; m represents the molar mass of the target compound, g/mol;22.4 represents the molar volume of gas in the standard state (273.15K, 101.325kPa), L/mol; f represents the dilution factor.
The quantification of the remaining target compounds was quantified by the internal standard method and calculated according to the formula (6).
Figure BDA0003739165040000181
In the formula: ρ is a unit of a gradient x Represents the concentration of the target compound in the sample,. Mu.g/m 3; a. The X Representing a response value of the target compound quantification ion; a. The IS Expressing the response value of the ion quantified by the internal standard substance; rho IS Represents the mole fraction of the internal standard in the sample, nmol/mol;
Figure BDA0003739165040000182
represents the average relative response factor of the target compound; m represents the molar mass of the target compound, g/mol;22.4 represents the molar volume of gas in the standard state (273.15K, 101.325kPa), L/mol; f represents the dilution factor.
The drawing of the standard curve and the data processing and analysis of the sample are completed in a data processing system as shown in fig. 1, and a spectrogram and a data analysis system are operated in the data processing system.
In this example, the order of peak appearance, the quantitative ion, and the auxiliary ion of the target compound are shown in table 2:
TABLE 2 order of appearance of peaks and quantitative ions, auxiliary ions of the target Compounds
Figure BDA0003739165040000183
Figure BDA0003739165040000191
Figure BDA0003739165040000201
Figure BDA0003739165040000211
By using the method, under the specified chromatographic conditions, the GC-FID chromatogram of 5C 2-C3 target compounds at the concentration point of 2ppm is shown in figure 4, and the GC-MS total ion flow chart of 112 other target compounds at the concentration point of 2ppm is shown in figure 5.
Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.

Claims (10)

1. The detection device for the volatile organic compounds in the fixed pollution source waste gas is characterized by comprising a vacuum bottle, a quantitative loop sample introduction device, a gas cold trap concentrator, a gas chromatography-mass spectrometer and a data processing system which are sequentially connected; the vacuum bottle is used for collecting waste gas of a fixed pollution source, the quantitative ring sampling device is used for performing quantitative ring collection on the waste gas of the fixed pollution source in the vacuum bottle and sampling the waste gas to a third-stage cold trap of the gas cold trap concentrator for focusing, and the gas cold trap concentrator sweeps the focused waste gas of the fixed pollution source into the gas chromatography-mass spectrometer by using carrier gas; the gas chromatography-mass spectrometer is used for carrying out gas chromatography separation on the waste gas of the fixed pollution source, wherein a hydrogen flame ionization detector is used for detecting C2-C3 target compounds, a mass spectrometer is used for detecting the rest target compounds, and detection data are sent to a data processing system for data analysis.
2. The detecting device according TO claim 1, wherein the volatile organic compounds include 117 species, including 57 species of PAMS standard gas, 13 species of aldehyde ketone compounds, and 47 species of TO-15 standard gas.
3. The device according to claim 2, wherein the volatile organic compound comprises acetylene, ethylene, propylene, n-butene, butadiene, trans-2-butene, cis-2-butene, 1-pentene, 2-methyl-1,3-butadiene, trans-2-pentene, cis-2-pentene, 1-hexene, ethane, propane, isobutane, n-butane, isopentane, n-pentane, 2,2-dimethylbutane, cyclopentane, 2,3-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexane, methylcyclopentane, 2,4-dimethylpentane, cyclohexane, 2-methylhexane, 2,3-dimethylpentane, 3-methylhexane, 2,2,4 trimethylpentane, n-heptane, methylcyclohexane, 3264 zxft-trimethylpentane, 2-methylheptane, 3-methylheptane, n-octane, n-nonane, decane, undecane, dodecane, benzene, toluene, m-toluene, p-xylene, styrene, o-xylene, cumene, benzaldehyde, n-propylbenzene, 1-ethyl-3-methylbenzene, 1-ethyl-4-methylbenzene, 1,3,5-trimethylbenzene, 1-ethyl-2-methylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, 1,4-diethylbenzene, 1,3-diethylbenzene, naphthalene, acetaldehyde, acrolein, acetone, propionaldehyde, isopropanol, methacrolein, methyl tert-butyl ether, vinyl acetate, n-butyraldehyde, 2-butanone, ethyl acetate, tetrahydrofuran, crotonaldehyde, valeraldehyde, 1,4-dioxane, methyl methacrylate, <xnotran> 4- -2- ,2- , , , , , , 3272 zxft 3272- -3424 zxft 3424- , , , , , 3535 zxft 3535- , , 3584 zxft 3584- -4284 zxft 4284- , -5325 zxft 5325- , 5623 zxft 5623- , 6262 zxft 6262- , , 3256 zxft 3256- , 3456 zxft 3456- , , 3838 zxft 3838- , , , -5749 zxft 5749- -1- , -6595 zxft 6595- , 6898 zxft 6898- , , 3428 zxft 3428- , , , , 3476 zxft 3476- , , 3734 zxft 3734- , , , 3757 zxft 3757- , 5852 zxft 5852- -3575 zxft 3575- , . </xnotran>
4. The detection device according to claim 1, wherein the quantitative loop sample injection device has functions of automatic quantitative sampling and automatic internal standard addition, and can realize automatic sample injection of samples in the vacuum bottle.
5. The detection device according to claim 1, wherein the gas cold trap concentrator has functions of automatic quantitative sampling and automatic addition of standard use gas and internal standard use gas, and has three-stage cold traps, and the third-stage cold trap is cooled to-190 ℃.
6. The detection apparatus according to claim 1, wherein in the gas chromatograph-mass spectrometer, the gas chromatograph is capable of performing electronic pressure control on the carrier gas, and the column oven has a temperature programming function; the mass spectrometer has a 70eV electron bombardment ion source, and has the functions of NIST mass spectrum gallery, manual/automatic tuning, data acquisition, quantitative analysis and spectral gallery retrieval.
7. A method for using the detection device of any one of claims 1 to 6, characterized by comprising the following steps:
s1, cleaning a vacuum bottle by using a vacuum bottle cleaning device, collecting a fixed pollution source waste gas sample by using one cleaned vacuum bottle, and collecting a bottle of internal standard use gas by using the other cleaned vacuum bottle;
s2, collecting a fixed pollution source waste gas sample collected in a vacuum bottle through a sample quantitative ring in a quantitative ring sampling device, collecting corresponding internal standard use gas through an internal standard quantitative ring in the quantitative ring sampling device, and focusing through a third-stage cold trap of a gas cold trap concentrator;
s3, blowing the mixture into a gas chromatography-mass spectrometer for separation by using carrier gas, detecting C2-C3 target compounds by using a hydrogen flame ionization detector, detecting the rest target compounds by using a mass spectrometer, and analyzing sample data by using a data processing system; C2-C3 target compounds are qualitative by retention time and quantitative by an external standard method; and comparing the retention time and the mass spectrogram of other target compounds with the standard substances for qualitative determination, and quantifying by an internal standard method.
8. The method according to claim 7, wherein in step S2, the quantitative loop sample injection device has 10 inlet and outlet positions, wherein the No. 1 position, the No. 2 position, the No. 3 position, the No. 4 position, the No. 5 position, the No. 6 position, the No. 7 position, the No. 8 position, the No. 9 position and the No. 10 position are sequentially arranged in a circle at equal intervals; the operation modes of the quantitative loop sample introduction device and the gas cold trap concentrator are divided into two modes, namely a sampling mode and a sample introduction mode;
in a sampling mode, a sample flows in through the No. 1 position, flows into the sample quantitative ring through the No. 2 position, fills the sample quantitative ring and discharges redundant samples through the No. 6 position and the No. 5 position in sequence; the internal standard enters from the No. 4 position by using gas, flows into the internal standard quantitative ring through the No. 3 position, fills the internal standard quantitative ring and discharges redundant gas through the No. 9 position and the No. 10 position in sequence; carrier gas enters from the No. 8 position and enters a third-stage cold trap of the gas cold trap concentrator through the No. 7 position for focusing;
in a sample introduction mode, a sample enters from the No. 1 position and enters the sample quantitative ring through the No. 2 position, and meanwhile, redundant samples are discharged through the No. 10 position; injecting the internal standard from the No. 4 position by using gas, and discharging redundant gas from the No. 5 position; and carrier gas enters through the No. 8 position, enters the internal standard quantitative ring through the No. 9 position, pushes the internal standard gas to sequentially enter the No. 3 position and the No. 2 position, then enters the sample quantitative ring, pushes the sample to sequentially enter the No. 6 position and the No. 7 position, and finally enters the third-stage cold trap of the gas cold trap concentrator for focusing.
9. The method of claim 7, wherein the standard curve required for analysis by the data processing system is specifically plotted by: according to the sampling process of the waste gas sample of the fixed pollution source, 1mL of standard use gas is respectively extracted from 0.10 mu mol/mol, 0.40 mu mol/mol, 0.80 mu mol/mol, 1.2 mu mol/mol and 2.00 mu mol/mol to enter a quantitative ring of a quantitative ring sampling device, 0.25mL of 1.00 mu mol/mol internal standard use gas is correspondingly extracted, the internal standard use gas enters a gas chromatography-mass spectrometer for measurement after being focused by a third-stage cold trap of a gas cold trap concentrator, and a data processing system is used for drawing a standard curve;
sequentially measuring from low concentration to high concentration according to instrument reference conditions;
drawing a standard curve by taking the concentration of the C2-C3 target compound as an abscissa and the response value of a chromatographic peak as an ordinate;
drawing a standard curve by adopting an average relative response factor method for the rest target compounds, calculating relative response factors according to a formula (1), and calculating average relative response factors of all standard concentration points of the target compounds according to a formula (2);
Figure FDA0003739165030000051
in the formula: RRF i Representing the relative response factor of the target compound at the i point in the standard series; a. The i Representing the response value of the quantitative ion of the target compound at the ith point in the standard series; a. The ISi Expressing the response value of the quantitative ion in the ith point in the standard series; rho IS Represents the mole fraction of the internal standard in the standard series, nmol/mol; rho i Represents the mol fraction of the target compound at the i point in the standard series, nmol/mol;
average relative response factor of target compound
Figure FDA0003739165030000052
The calculation is performed according to equation (2):
Figure FDA0003739165030000053
in the formula:
Figure FDA0003739165030000054
represents the average relative response factor of the target compound; RRF i Representing the relative response factor of the target compound at the i point in the standard series; n represents a standard series of points;
the standard curve requires that the relative standard deviation of the relative response factors should be less than or equal to 30%, or a linear standard curve established by the least square method requires that the correlation coefficient be greater than or equal to 0.990.
10. The method of claim 7, wherein in step S3, the quantification of the C2-C3 target compound is quantified by external standard method, calculated according to equation (5):
Figure FDA0003739165030000055
in the formula: rho x Represents the concentration of the target compound in the sample,. Mu.g/m 3 ；ρ a Represents the molar fraction of the target compound obtained from the standard curve, nmol/mol; m represents the molar mass of the target compound, g/mol;22.4 represents the molar volume of the gas in the standard state, L/mol; f represents dilution multiple;
quantification of the remaining target compounds was quantified by internal standard method, calculated according to equation (6):
Figure FDA0003739165030000061
in the formula: rho x Represents the concentration of the target compound in the sample,. Mu.g/m 3; a. The X Representing the response value of the quantitative ions of the target compound; a. The IS Expressing the response value of the ion quantified by the internal standard substance; rho IS Represents the mole fraction of the internal standard in the sample, nmol/mol;
Figure FDA0003739165030000062
represents the average relative response factor of the target compound; m represents the molar mass of the target compound, g/mol;22.4 represents the molar volume of the gas in the standard state, L/mol; f represents the dilution factor.
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