CN112114064A - Method for detecting volatile organic compounds in furniture - Google Patents

Method for detecting volatile organic compounds in furniture Download PDF

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CN112114064A
CN112114064A CN202010909487.0A CN202010909487A CN112114064A CN 112114064 A CN112114064 A CN 112114064A CN 202010909487 A CN202010909487 A CN 202010909487A CN 112114064 A CN112114064 A CN 112114064A
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gas
furniture
temperature
volatile organic
sampling
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高翠玲
韩智峰
刘萌萌
李桂晓
唐孔科
熊大伟
吴恩凯
张楠
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Shandong Institute for Product Quality Inspection
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/08—Preparation using an enricher
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8624—Detection of slopes or peaks; baseline correction
    • G01N30/8631—Peaks
    • G01N30/8634—Peak quality criteria

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Abstract

The invention discloses a method for detecting volatile organic compounds in furniture, which comprises the steps of placing the furniture to be detected in a climate chamber, sampling after 20 +/-0.5 hours, wherein the sampling time is 1 +/-0.5 hours, connecting a washed and vacuumized Suma tank with the climate chamber, carrying out constant-current sampling on volatile organic gases, after the sampling is finished, pressurizing and diluting the volatile gases in the Suma tank by using high-purity nitrogen to enable the pressure in the Suma tank to reach 101kPa, transferring the volatile gases in the Suma tank into a cold trap concentrator for concentration, adding an internal standard for using gas, and detecting the gas by using a gas mass spectrometer after the gas is concentrated. The climate chamber is adopted to simulate daily environment, released volatile organic compounds are collected into the vacuum suma tank, loss of the volatile organic compounds in furniture in the sampling process is greatly reduced, integrity of the furniture is kept to the greatest extent, and meanwhile, various volatile organic compounds are screened and detected, so that the detection limit is low, the accuracy rate is high, the operation is strong, and the speed is high.

Description

Method for detecting volatile organic compounds in furniture
Technical Field
The invention belongs to the technical field of indoor environment inspection, and particularly relates to a method for detecting volatile organic compounds in furniture.
Background
With the continuous development of the home decoration market, various problems in home decoration are followed. Especially indoor environmental pollution, has attracted more and more attention due to its harmfulness to human bodies. The VOC, the source of indoor environmental pollution, also gradually floats out of the water. VOCs are organic (carbon-based) gases, also known as hydrocarbons, emitted by many different products. The evaporation of VOC is caused by sufficient pressure. Common sources of volatile organic compounds in the room are decorative building materials, carpets, printers, furniture, paint thinners, glues, cosmetics and certain sprays, and also plastic products. According to the environmental protection agency's report, if there is not enough ventilation equipment to circulate the air and VOC exists indoors, the indoor air pollution level will be as much as 10 times more severe than the outdoor air.
The main components of VOC are: hydrocarbons, halogenated hydrocarbons, oxygen hydrocarbons and nitrogen hydrocarbons, which include: benzene series, organic chloride, freon series, organic ketone, amine, alcohol, ether, ester, acid and petroleum hydrocarbon compound. VOC is the abbreviation of volatile organic compounds, and the chemical substances (except heavy metals) harmful to human bodies in the wall paint are VOC. These volatile organic compounds include formaldehyde, ammonia, ethylene glycol, esters, and the like. When the VOC in a room reaches a certain concentration, symptoms such as headache, nausea, vomiting, hypodynamia and the like can be caused, and even convulsion and coma can be caused in severe cases, so that the liver, the kidney, the brain and the nervous system are injured, and serious consequences such as hypomnesis and the like are caused.
With the rapid development of economy, the furniture industry in China is rapidly developed, and the innovation of the furniture product processing technology and the application of novel materials are accelerated. Meanwhile, certain raw and auxiliary materials, production and processing processes and the like in the furniture product can bring certain harmful substances into the furniture product in the production process, wherein the harmful substances comprise volatile organic substances which are increasingly concerned by consumers. At present, no special detection equipment for the harmful substances in furniture products exists in the market, so that the establishment of a detection method for the volatile organic compounds in the furniture is very important.
On the other hand, the furniture products belong to a large number of durable consumer goods, if the traditional detection method is adopted to carry out destructive detection on the furniture products, unnecessary waste is caused, the enterprise burden and the operation cost are increased, and meanwhile, the result cannot truly reflect the types and the content conditions of volatile organic compounds released by the furniture under daily use conditions. The thermal analysis-gas chromatography-mass spectrometry combined method can only collect a small part of volatile organic compounds, the obtained information is limited, the sampling tube has high purchase cost and short service life, is easily influenced by temperature and humidity, and has the defects of short retention time after collection, easy loss and great limitation if the content of the substance to be detected is high and easy to penetrate. The aldehyde ketone sampling tube can only collect aldehyde ketone compounds by matching with the liquid chromatography, and the application range is quite limited.
Disclosure of Invention
Aiming at the problems that the existing detection method in the prior art is limited in information acquisition, high in cost and easy to damage furniture, the invention discloses a method for detecting volatile organic compounds in furniture.
The invention is realized by the following technical scheme:
the furniture to be detected is placed in a climate cabin, released volatile organic compounds are collected into a vacuum Suma tank, and the volatile organic compounds in the Suma tank are concentrated and transferred to a gas chromatograph-mass spectrometer for detection.
Further, the detection method comprises the following steps:
(1) placing furniture to be detected in a climate chamber, and sampling after 20 +/-0.5 h, wherein the sampling time is 1 +/-0.5 h;
(2) connecting the cleaned and vacuumized suma tank with a climate chamber, carrying out constant-flow sampling on volatile organic gas, and after sampling is finished, pressurizing and diluting the volatile organic gas by using high-purity nitrogen to enable the pressure in the suma tank to reach 101 kPa;
(3) transferring volatile gas in the Suma tank into a cold trap concentrator for concentration, adding internal standard gas for use, and detecting the gas by using a gas chromatograph-mass spectrometer after the gas is concentrated.
Further, the furniture is pretreated before being placed in a climate chamber, the pretreatment method comprises the step of assembling the furniture according to a pattern which is most beneficial to the release of harmful substances, the pretreatment time is 120 +/-2 hours, the temperature is 23 +/-2 ℃, the relative humidity is 45 +/-10%, the distance between samples is less than 300mm, and the concentration of formaldehyde between the samples is less than or equal to 0.10mg/m3The TVOC concentration is less than or equal to 0.60mg/m3。
Further, the bearing rate of the climate chamber in the step (1) is 0.075-0.3, the temperature is 23 +/-2 ℃, the relative humidity is 45 +/-10%, and the aldehyde concentration in the feeding air is less than or equal to 0.10mg/m3The TVOC concentration is less than or equal to 0.60mg/m3(ii) a And (3) humidifying and cleaning the suma tank in the step (2) before use, wherein the cleaning temperature is 80 ℃, and vacuumizing after cleaning.
Further, the internal standard gas is more than one of monobromo-chloromethane, 1, 2-difluorobenzene and chlorobenzene-d 5.
Further, the amount of the volatile gas in the suma tank transferred to the cold trap concentrator in the step (3) is 50-1000 mL, preferably 400 mL; the internal standard used gas concentration was 100 nmol/mol.
The detection method according to claim 2, wherein the size of the suma tank is 6L, the sampling flow rate is 90mL/min, and the sampling time is 1 hour.
Further, the collection conditions of the cold trap concentrator are as follows: the trapping temperature of the primary cold trap is-150 ℃, the trapping flow rate is 100mL/min, the desorption temperature is 10 ℃, the valve temperature is 100 ℃, the baking temperature is 150 ℃, and the baking time is 15 min; the trapping temperature of the secondary cold trap is-15 ℃, the trapping flow rate is 10mL/min, the trapping time is 5min, the resolving temperature is 180 ℃, the resolving time is 3.5min, the baking temperature is 190 ℃, and the baking time is 15 min; the third-stage focusing temperature is-160 deg.C, the resolving time is 2.5min, the baking temperature is 200 deg.C, and the baking time is 5 min;
the gas chromatography-mass spectrometry conditions are as follows: heating a quartz capillary chromatographic column with a polarity index of less than 10 by a program at 40 ℃ for 1min, heating to 100 ℃ at 3 ℃/min, heating to 250 ℃ at 10 ℃/min, and keeping for 10min, wherein the carrier gas is helium and the flow rate is 1.2 mL/min; the chromatography-mass spectrometry interface temperature is 260 ℃; the ion source is an electron ionization source and the temperature is 260 ℃; ionization energy is 70 eV; the mass analyzer is a quadrupole mass analyzer; the mass scanning range is 25-450 amu; the scanning mode is a full scanning mode.
Further, the detection method is used for qualitatively and quantitatively analyzing volatile organic compounds in furniture.
And (3) before the volatile organic gas in the furniture is concentrated and detected, measuring the pressure in the Suma tank by using a vacuum pressure gauge. If the pressure in the tank is less than 83kPa, the tank is pressurized to 101kPa with high-purity nitrogen gas, and the dilution factor is calculated according to the formula (1):
Figure 807522DEST_PATH_IMAGE001
in the formula: f is dilution multiple, dimensionless;
Xa-tank pressure before dilution, kPa;
Ya-tank pressure after dilution, kPa.
Calculation of relative impact factor (RRF) of objects in furniture: respectively extracting 50mL, 100mL, 200mL, 400mL, 600mL and 800mL of standard use gas by using an atmospheric preconcentrator, simultaneously adding 50mL of internal standard use gas, preparing a standard series of which the concentrations of the targets are 1.25nmol/mol, 2.5nmol/mol, 5.0nmol/mol, 10.0nmol/mol, 15.0nmol/mol and 20.0nmol/mol respectively, wherein the concentration of the internal standard substance is 12.5nmol/mol, the sampling volume of the atmospheric preconcentrator is 400mL, sequentially measuring from low concentration to high concentration according to the instrument reference conditions in the step 5, calculating the relative influence factor of the target according to the formula (2), and calculating the average relative influence factor (RRF) of all standard concentration points of the target according to the formula (3);
Figure 508018DEST_PATH_IMAGE002
in the formula: RRF-relative response factor of target, dimensionless;
Ax-target compound quantification of ion peak area;
Ais-internal standard compound quantification of ion peak area;
ψis-the molar fraction of the internal standard compound, nmol/mol;
ψx-the molar fraction of the target compound, nmol/mol.
Figure 84493DEST_PATH_IMAGE003
In the formula: RRF-mean relative response factor of the target, dimensionless;
RRFi-the relative response factor of the target at point i in the standard series is dimensionless;
n-standard series of points.
The qualitative analysis of volatile organic compounds in furniture is determined in a full-scan manner, and is characterized by the relative retention time of a target object in a sample, the abundance ratio between auxiliary qualitative ions and quantitative ions and the target object comparison in a standard. The relative retention time of the compound of interest in the sample should be within ± 3.0% of the relative retention time of that compound in the calibration series. The relative deviation of the auxiliary qualitative ion and quantitative ion peak area ratio (Q sample) of the target compound in the sample and the auxiliary qualitative ion and quantitative ion peak area ratio of the standard series target compound is controlled within +/-30%.
Calculating the relative retention time of the target according to the formula (4):
Figure 479702DEST_PATH_IMAGE004
in the formula: RRT — target compound relative retention time, dimensionless;
RTcretention time of target compound, min;
RTisretention time of internal standard, min.
Calculate the average Relative Retention Time (RRT) according to equation (5): relative retention time averages for the same target compound in the standard series.
Figure 825233DEST_PATH_IMAGE005
In the formula: RRT — average relative retention time of target, dimensionless;
RRT i-the relative retention time of the target at point i in the standard series, dimensionless;
n-standard series of points.
Calculating the area ratio of auxiliary qualitative ion peak area to auxiliary quantitative ion peak area according to formula (6)
Figure 195166DEST_PATH_IMAGE006
In the formula: q-the ratio of the auxiliary qualitative ion peak area to the auxiliary quantitative ion peak area;
At-quantifying the ion peak area;
Aq-auxiliary qualitative ion peak area.
And (3) quantitatively analyzing the volatile organic compounds in the furniture by adopting an average relative response factor to carry out quantitative calculation, and referring to appendix C for quantitative ions of the target substances and corresponding relations between the target substances and the internal standard substances. The content of the target in the sample (. mu.g/m 3) was calculated according to formula (7).
Figure 258936DEST_PATH_IMAGE007
In the formula: rho-concentration of target in sample, μ g/m3；
A x-quantitative ion peak area of target in sample;
A is-quantitative ion peak area of the internal standard in the sample;
ψis-the molar fraction of internal standard in the sample, nmol/mol;
RRF-mean relative response factor of the target, dimensionless;
f is dilution multiple, dimensionless;
m is the molar mass of the target, g/mol;
22.4-molar volume of gas in the standard state (273.15K, 101.325 kPa), L/mol.
Advantageous effects
(1) The climate chamber is adopted to simulate the daily environment, and the released volatile organic compounds are collected into the vacuum suma tank, so that the loss of the volatile organic compounds in the furniture in the sampling process is greatly reduced, and the integrity of the furniture is kept to the greatest extent;
(2) the invention can screen and detect various volatile organic compounds simultaneously, has low detection limit, high accuracy, strong operability and high speed, and can realize qualitative and quantitative detection of various volatile organic compounds in furniture.
Drawings
FIG. 1 shows a gas chromatography-mass spectrometry ion chromatogram of volatile benzene compounds in furniture (wherein, 1.RT 6.88, benzene; 2. RT 9.83, toluene; 3. RT 12.70, vinylcyclohexene; 4. RT 13.66, ethylbenzene; 5. RT 13.97, p-xylene; 6. RT 13.97, m-xylene; 7. RT 14.10, phenylacetylene; 8. RT 14.87, styrene; 9. RT 15.11, o-xylene; 10. RT 16.69, isopropylbenzene; 11.RT 18.15, n-propylbenzene; 12. RT 18.54, 3-ethyltoluene; 13. RT 18.93, 1,3, 5-trimethylbenzene; 14. RT 19.41, α -phenylpropylene; 15. RT 19.43, 2-ethyltoluene; 16. RT 20.03, vinyltoluene; 17. RT 21.21, 1,2, 4-trimethylbenzene; 18. RT 21.51, 1,2, 3-trimethylbenzene; 19. RT 21.74, 1-isopropyl-4-methylbenzene; 20. RT 22.28, indene; 21. RT 22.31, 1-isopropyl-2-methylbenzene; 22. RT 23.01, n-butylbenzene; 23. RT 25.05, 1,2,4, 5-tetramethylbenzene; 24. RT 26.11, 1, 3-diisopropylbenzene; 25. RT 26.61, 1, 4-diisopropylbenzene; 26. RT 26.67, naphthalene; 27. RT 29.85, 4-phenylcyclohexene; 28. RT 31.97, octylbenzene, RT retention time);
FIG. 2 is a gas chromatography-mass spectrometry selected ion chromatogram of volatile alcohols in furniture (1. RT 4.85, 2-propanol; 2. RT 5.05, tert-butyl alcohol (2-methyl-2-propanol); 3. RT 5.32, 1-propanol; 4. RT 6.26.2-methyl-1-propanol; 5. RT 6.92, 1-butanol; 6. RT 14.05, 1-hexanol; 7. RT 14.57, cyclohexanol; 8. RT 19.19, phenol; 9. RT 21.45, benzyl alcohol; 10. RT 21.96, 2-ethyl-1-hexanol; 11.RT 23.6, 1-octanol; 12. RT 32.55, butylhydroxytoluene, RT retention time);
FIG. 3 is a gas chromatography-mass spectrometry ion chromatogram of volatile halogenated hydrocarbons in furniture (1. RT 4.29, carbon tetrachloride; 2. RT 5.06, dichloromethane; 3. RT 5.50, chloroform; 4. RT 6.05, 1, 1-dichloroethane; 5. RT 6.61, 1,1, 1-trichloroethane; 6. RT 7.78, trichloroethylene; 7. RT 8.66, dichloropropene; 8. RT 9.29, tetrachloroethylene; 9. RT 11.61, chlorobenzene; 10. RT 12.85, alpha-chlorotoluene; 11.RT 20.56, 1, 3-dichlorobenzene; 12. RT 20.58, 1, 4-dichlorobenzene; 13. RT 20.76, 1, 2-dichlorobenzene; 14. RT 23.13, 1, 2-dibromo-3-chloropropane; 15. RT 25.27, alpha-dichlorotoluene, RT is retention time);
FIG. 4 is a gas chromatography-mass spectrometry selective ion chromatogram of volatile terpenes in furniture (1. RT 17.81, alpha-pinene; 2. RT 18.47, camphene; 3. RT 19.79, beta-pinene; 4. RT 20.43, myrcene; 5. RT 21.52, carene; 6. RT 22.28, limonene; 7. RT 27.00, terpineol; 8. T31.50, longifolene; 9. RT 31.59, cedrene; 10. RT 31.60, cedrene; 11.RT 31.64, caryophyllene; 12. RT 31.83, thujoram, RT retention time);
FIG. 5 is a gas chromatography-mass spectrometry selective ion chromatogram of volatile alkanes in furniture (1. RT 5.80, 3-methylpentane; 2. RT 6.04, n-hexane; 3. RT 7.18, cyclohexane; 4. RT 8.18, n-heptane; 5. RT 8.82, methylcyclohexane; 6. RT 11.69, n-octane; 7. RT 21.32, n-decane; 8. RT 25.03, n-undecane; 9. RT 27.57, n-dodecane; 10. RT 31.13, n-tetradecane; 11.RT 33.80, n-hexadecane, RT retention time);
FIG. 6 is a gas chromatography-mass spectrometry selected ion chromatogram of volatile esters in furniture (1. RT 5.06, methyl acetate; 2. RT 5.59, vinyl acetate; 3. RT 6.00, ethyl acetate; 4. RT 6.88, isopropyl acetate; 5. RT 7.60, ethyl acrylate; 6. RT 8.09, propyl acetate; 7. RT 8.36, butyl formate; 8. RT 10.02, isobutyl acetate; 9. RT 11.50, butyl acetate; 10. RT 13.67, 2-methoxy-1-methyl ethyl acetate; 11.RT 15.08, butyl acrylate; 12. RT 25.96, 2-ethylhexyl acetate; 13. RT 27.82, 2-ethylhexyl acrylate; RT retention time);
FIG. 7 is a gas chromatography-mass selective ion chromatogram of other classes of volatile organic compounds in furniture (RT 9.42, N, N-dimethylformamide, RT retention time).
Detailed Description
Standard use gas: diluting the standard gas to 10nmol/mol by using a gas diluting device and high-purity nitrogen;
internal standard use gas: monobromomethane chloride with a concentration of 100nmol/mol, 1, 2-difluorobenzene, chlorobenzene-d 5.
In the embodiment of the invention, the nitrogen is high-purity nitrogen with the purity not less than 99.999 percent, and the helium is high-purity helium with the purity not less than 99.999 percent.
Gas chromatography-mass spectrometer (GC/MS) used in the examples of the present invention: is provided with a quality selection detector; the atmospheric preconcentrator has the functions of automatic quantitative sampling and automatic addition of standard gas and internal standard; the maximum dilution multiple of the gas diluter can reach 1000 times, and the concentrator automatically feeds a sample device; the tank cleaning device can pump the sampling tank to vacuum (less than 10 Pa), and has the functions of heating, humidifying and pressurizing cleaning. A Suma pot: the stainless steel sampling tank with inerted inner wall has a volume of 6L and a pressure resistance value of more than 241 kPa. The flow controller is matched with the Suma tank for use; the calibrated flowmeter can accurately control the flow, and the pore diameter of the filter is less than or equal to 10 mu m.
The internal standard used in example 1 of the present invention was monochloromethane monobromo, 1, 2-difluorobenzene, chlorobenzene-d 5, with a gas concentration of 100 nmol/mol.
The analysis conditions of the atmospheric preconcentrator in the following examples were:
primary cold trap: trapping temperature: -150 ℃; collecting flow rate: 100 mL/min; resolving temperature: 10 ℃; valve temperature: 100 ℃; baking temperature: 150 ℃; baking time: 15 min;
secondary cold trap: trapping temperature: -15 ℃; collecting flow rate: 10 mL/min; collecting time: 5 min; resolving temperature: 180 ℃; analysis time: 3.5 min; baking temperature: 190 ℃; baking time: 15 min;
and (3) three-stage focusing: focusing temperature: -160 ℃; analysis time: 2.5 min; baking temperature: 200 ℃; baking time: 5 min;
transmission line temperature: 120 ℃ is adopted.
GC conditions: a) quartz capillary chromatographic column: the polarity index is less than 10, the column length is 50-60 m, the inner diameter is 0.25 mm, and the film thickness is 0.25 mu m;
b) temperature rising procedure: keeping the temperature at 40 ℃ for 1min, then heating to 100 ℃ at the speed of 3 ℃/min, then heating to 250 ℃ at the speed of 10 ℃/min, and keeping the temperature for 10 min;
c) carrier gas: high-purity helium with the purity of more than or equal to 99.999 percent and the flow rate of 1.2 mL/min;
d) interface temperature of chromatography-mass spectrometry: 260 ℃;
e) an ion source: the temperature of the electron ionization source EI is 230 ℃;
f) ionization energy: 70 eV;
g) a mass analyzer: a quadrupole mass analyser;
h) mass scan range: (25-450) amu;
i) scanning mode: the full scan mode is selected.
Example 1
1. Pretreatment of
The furniture is put according to the pattern most beneficial to the release of harmful substances, the furniture is pretreated according to the whole piece, the surface is exposed in a pretreatment environment as far as possible, the pretreatment time is 120h, and the pretreatment environmental conditions are as follows: the temperature is 23 +/-2 ℃, the relative humidity is 45 +/-10%, the distance between samples is not less than 300mm, the concentration of formaldehyde between samples is less than 0.10mg/m3, and the concentration of TVOC is not more than 0.60mg/m 3.
Collection of VOC
Selecting a climate chamber, wherein the bearing rate is 0.15, and the air exchange rate is 1; the furniture sample is put into the climate chamber for 1h to collect the air in the chamber, and the formaldehyde, benzene, toluene and xylene are measured and recorded to be less than or equal to 0.005mg/m3 and the TVOC is less than or equal to 0.05mg/m 3;
putting the pretreated furniture into a climate chamber for experiment, and sampling the furniture sample after 20 hours in the climate chamber, wherein the sampling time is 1 +/-0.5 hours; the conditions of the climate chamber are: the temperature is 23 +/-2 ℃, the relative humidity is 45 +/-10%, and the air replacement rate is 0.5 +/-0.05 times/h: the air flow rate is 90mL/min, and the concentration of formaldehyde, benzene, toluene, xylene and TVOC in the sample air is as follows: formaldehyde is less than or equal to 0.006mg/m3The single VOC is less than or equal to 0.0056mg/m3、TVOC≤0.05mg/m3。
3. Suma pot sampling
Cleaning the Suma tank by using a tank cleaning device before the use of the Suma tank, humidifying the Suma tank in the cleaning process to reduce the active adsorption of the tank body, wherein the cleaning temperature is 80 ℃, and after the cleaning is finished, vacuumizing the Suma tank to less than 10Pa for later use;
connecting a cleaned and vacuumized suma tank with a climate chamber, installing a flow controller and a filter, opening a valve of the suma tank, starting constant-flow sampling, closing the valve after the sampling time corresponding to the set constant-flow of 90mL/min is reached, and sealing by using a sealing cap;
measuring the pressure in the Suma tank by using a vacuum pressure gauge, if the pressure in the Suma tank is less than 83kPa, pressurizing to 101kPa by using high-purity nitrogen, and the dilution multiple of the collected furniture volatile gas is the ratio of the pressure in the tank after dilution to the pressure in the tank before dilution;
the dilution factor was calculated according to formula (1):
Figure 457837DEST_PATH_IMAGE008
in the formula: f is dilution multiple, dimensionless;
Xa-tank pressure before dilution, kPa;
Ya-tank pressure after dilution, kPa;
the volatile gas collected in the suma jar can be detected immediately or stored at normal temperature for detection and analysis within 20 days.
4. Blank sample assay
And connecting the cleaned and vacuumized suma tank to a gas diluting device, opening a high-purity nitrogen valve, and closing the valve of the suma tank and the valve of the nitrogen tank after the pressure of the suma tank reaches 101 kPa. Taking 400mL of blank sample, concentrating by an atmosphere preconcentrator, and analyzing by gas chromatography-mass spectrometry.
5. Drawing a standard curve
Respectively extracting 50mL, 100mL, 200mL, 400mL, 600mL and 800mL of standard use gas by using a gas concentration cold trap concentrator, simultaneously adding 50mL of internal standard use gas, preparing standard series with the concentrations of targets of 1.25nmol/mol, 2.5nmol/mol, 5.0nmol/mol, 10.0nmol/mol, 15.0nmol/mol and 20.0nmol/mol, respectively, wherein the concentration of the internal standard substance is 12.5nmol/mol, and sequentially measuring in a gas chromatograph-mass spectrometer from low concentration to high concentration;
calculating a relative influence factor of the target according to the formula (2), and calculating an average relative influence factor (RRF) of all standard concentration points of the target according to the formula (3);
Figure 657874DEST_PATH_IMAGE009
in the formula: RRF-relative response factor of target, dimensionless;
Ax-target compound quantification of ion peak area;
Ais-internal standard compound quantification of ion peak area;
ψis-the molar fraction of the internal standard compound, nmol/mol;
ψx-the molar fraction of the target compound, nmol/mol;
Figure 651238DEST_PATH_IMAGE010
in the formula: RRF-mean relative response factor of the target, dimensionless;
RRFi-the relative response factor of the target at point i in the standard series is dimensionless;
n-standard series of points.
6. Sample analysis
Connecting the sample gas in the diluted suma tank to a gas concentration cold trap concentrator, taking 400mL of the gas in the diluted suma tank, adding 50mL of internal standard use gas with the concentration of 100nmol/mol, concentrating the atmosphere preconcentrator, and detecting by using a gas chromatograph-mass spectrometer after concentration.
7. Qualitative analysis
The assay is performed in a full scan mode, and is characterized by the relative retention time of the target in the sample, the abundance ratio between the auxiliary qualitative and quantitative ions, and the comparison of the target in the standard. The relative retention time of the compound of interest in the sample should be within ± 3.0% of the relative retention time of that compound in the calibration series. The relative deviation of the auxiliary qualitative ion and quantitative ion peak area ratio (Qsample) of the target compound in the sample and the auxiliary qualitative ion and quantitative ion peak area ratio (Qstandard) of the standard series target compound is controlled within +/-30%;
calculating the relative retention time of the target according to the formula (4):
Figure 405567DEST_PATH_IMAGE011
in the formula: RRT — target compound relative retention time, dimensionless;
RTcretention time of target compound, min;
RTis-retention time of internal standard, min;
calculate the average Relative Retention Time (RRT) according to equation (5): relative retention time averages for the same target compound in the standard series;
Figure 188584DEST_PATH_IMAGE012
in the formula: RRT — average relative retention time of target, dimensionless;
RRT i-the relative retention time of the target at point i in the standard series, dimensionless;
n-standard series points;
calculating the area ratio of auxiliary qualitative ion peak area to auxiliary quantitative ion peak area according to formula (6)
Figure 711969DEST_PATH_IMAGE013
In the formula: q-the ratio of the auxiliary qualitative ion peak area to the auxiliary quantitative ion peak area;
At-quantifying the ion peak area;
Aq-auxiliary qualitative ion peak area.
8. Quantitative analysis
And performing quantitative calculation by using the average relative response factor, and referring to appendix C for quantitative ions of the target substances and the corresponding relation between each target substance and the internal standard substance. The content of the target in the sample (. mu.g/m 3) was calculated according to formula (7).
Figure 672972DEST_PATH_IMAGE014
In the formula: rho-concentration of target in sample, μ g/m3；
A x-quantitative ion peak area of target in sample;
A is-quantitative ion peak area of the internal standard in the sample;
ψis-the molar fraction of internal standard in the sample, nmol/mol;
RRF-mean relative response factor of the target, dimensionless;
f is dilution multiple, dimensionless;
m is the molar mass of the target, g/mol;
22.4-molar volume of gas in the standard state (273.15K, 101.325 kPa), L/mol.
The detection method in example 1 is suitable for qualitative and quantitative analysis of one or more volatile organic gases in furniture, the list of target volatile organic compounds in furniture is shown in tables 1-8, and the chromatogram and retention time of the target volatile organic compounds (standard substances) in furniture are shown in fig. 1-7.
Method characteristics
Detection limit
The detection, quantitation and linear range of volatile organic compounds in furniture are shown in tables 9-15.
Precision degree
The absolute difference between two independent test results obtained from tests performed independently of each other on the same test object in a short time in the same laboratory by the same operator using the same equipment according to the same test method is not more than 10% of the arithmetic mean of the two measured values, on the premise that 10% more than the arithmetic mean of the two measured values is not more than 5%.
Repeatability of
The relative deviation of the results of these two measurements in the same run was less than 10%.
TABLE 1 list of target benzene series volatile organic compounds in furniture
Figure 914598DEST_PATH_IMAGE015
TABLE 2 furniture list of volatile organics in target alcohols
Figure 986459DEST_PATH_IMAGE016
TABLE 3 list of volatile organics in furniture for target halogenated hydrocarbons
Figure 629930DEST_PATH_IMAGE017
TABLE 4 list of volatile organics of target terpenes in furniture
Figure 246987DEST_PATH_IMAGE018
TABLE 5 list of target alkane volatile organics in furniture
Figure 975909DEST_PATH_IMAGE019
TABLE 6 list of target aldehydes and ketones of volatile organic compounds in furniture
Figure 851461DEST_PATH_IMAGE020
TABLE 7 list of target ester volatile organics in furniture
Figure 349438DEST_PATH_IMAGE021
TABLE 8 list of other volatile organics in furniture
Figure 652243DEST_PATH_IMAGE022
TABLE 9 detection, quantitation and Linear Range of volatile benzene Compounds in furniture
Figure 602882DEST_PATH_IMAGE023
TABLE 10 detection, quantitation, and Linear Range of volatile alcohols in furniture
Figure 534322DEST_PATH_IMAGE024
TABLE 11 detection, quantitation and Linear Range of volatile halogenated hydrocarbons in furniture
Figure 886806DEST_PATH_IMAGE025
TABLE 12 detection, quantitation, and Linear Range of volatile terpenes in furniture
Figure 626092DEST_PATH_IMAGE026
TABLE 13 detection, quantitation, and Linear Range of volatile alkanes in furniture
Figure 64027DEST_PATH_IMAGE027
TABLE 14 detection, quantitation, and Linear Range of volatile esters in furniture
Figure 15802DEST_PATH_IMAGE028
TABLE 15 detection limits, quantitation limits, and Linear Range of other classes of volatile Compounds in furniture
Figure 488372DEST_PATH_IMAGE029
。

Claims (10)

1. The method for detecting the volatile organic compounds in the furniture is characterized in that the furniture to be detected is placed in a climate chamber, the released volatile organic compounds are collected into a vacuum Suma tank, and the volatile organic compounds in the Suma tank are concentrated and then transferred to a gas chromatograph-mass spectrometer for detection.
2. The detection method according to claim 1, characterized in that the detection method comprises the following steps:
(1) placing furniture to be detected in a climate chamber, and sampling after 20 +/-0.5 h, wherein the sampling time is 1 +/-0.5 h;
(2) connecting the cleaned and vacuumized suma tank with a climate chamber, carrying out constant-flow sampling on volatile organic gas, and after sampling is finished, pressurizing and diluting the volatile organic gas by using high-purity nitrogen to enable the pressure in the suma tank to reach 101 kPa;
(3) transferring volatile gas in the Suma tank into a cold trap concentrator for concentration, adding internal standard gas for use, and detecting the gas by using a gas chromatograph-mass spectrometer after the gas is concentrated.
3. The detection method according to claim 2, wherein the furniture is pre-treated before being placed in the climate chamber, the pre-treatment method is to assemble the furniture according to a pattern which is most beneficial to the release of harmful substances, the pre-treatment time is 120 plus or minus 2h, the temperature is 23 plus or minus 2 ℃, the relative humidity is 45 plus or minus 10 percent, the distance between samples is less than 300mm, and the concentration of formaldehyde between samples is less than or equal to 0.10mg/m3The TVOC concentration is less than or equal to 0.60mg/m3。
4. The detection method according to claim 2, wherein the load-bearing rate of the climate chamber in the step (1) is 0.075-0.3, the temperature is 23 ± 2 ℃, the relative humidity is 45 ± 10%, and the aldehyde concentration in the feeding air is less than or equal to 0.10mg/m3The TVOC concentration is less than or equal to 0.60mg/m3(ii) a Humidifying and cleaning the Suma tank in the step (2) before use, wherein the cleaning temperature is 80 ℃,after the cleaning, the vacuum is pumped.
5. The detection method according to claim 2, wherein the internal standard gas is one or more of monochloromethane monobromo, 1, 2-difluorobenzene and chlorobenzene-d 5.
6. The detection method according to claim 2, wherein the amount of the volatile gas in the suma tank transferred to the cold trap concentrator in the step (3) is 50-1000 mL; the internal standard used gas concentration was 100 nmol/mol.
7. The detection method according to claim 6, wherein the amount of sample volatile gas in the suma tank transferred to the cold trap concentrator is 400 mL.
8. The detection method according to claim 2, wherein the size of the suma tank is 6L, the sampling flow rate is 90mL/min, and the sampling time is 1 hour.
9. The detection method according to claim 2, wherein the collection conditions of the cold trap concentrator are as follows: the trapping temperature of the primary cold trap is-150 ℃, the trapping flow rate is 100mL/min, the desorption temperature is 10 ℃, the valve temperature is 100 ℃, the baking temperature is 150 ℃, and the baking time is 15 min; the trapping temperature of the secondary cold trap is-15 ℃, the trapping flow rate is 10mL/min, the trapping time is 5min, the resolving temperature is 180 ℃, the resolving time is 3.5min, the baking temperature is 190 ℃, and the baking time is 15 min; the third-stage focusing temperature is-160 deg.C, the resolving time is 2.5min, the baking temperature is 200 deg.C, and the baking time is 5 min;
the gas chromatography-mass spectrometry conditions are as follows: heating a quartz capillary chromatographic column with a polarity index of less than 10 by a program at 40 ℃ for 1min, heating to 100 ℃ at 3 ℃/min, heating to 250 ℃ at 10 ℃/min, and keeping for 10min, wherein the carrier gas is helium and the flow rate is 1.2 mL/min; the chromatography-mass spectrometry interface temperature is 260 ℃; the ion source is an electron ionization source and the temperature is 260 ℃; ionization energy is 70 eV; the mass analyzer is a quadrupole mass analyzer; the mass scanning range is 25-450 amu; the scanning mode is a full scanning mode.
10. The detection method of claim 2, wherein the detection method is used for qualitative and quantitative analysis of volatile organic compounds in furniture.
CN202010909487.0A 2020-09-02 2020-09-02 Method for detecting volatile organic compounds in furniture Pending CN112114064A (en)

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CN113917055A (en) * 2021-09-26 2022-01-11 山东省济南生态环境监测中心 Method for improving accuracy of detecting non-methane total hydrocarbons in air by using gas in Suma tank
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CN115343381A (en) * 2022-07-11 2022-11-15 中国计量科学研究院 Detection device and method for volatile organic compounds in waste gas of fixed pollution source
CN115201367B (en) * 2022-07-11 2024-01-26 中国计量科学研究院 Method for detecting sulfur-containing organic compounds in pollution sources
CN115236239A (en) * 2022-08-09 2022-10-25 多特瑞(上海)商贸有限公司 Method for detecting content of alpha-copal in schisandra essential oil
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