CN103675134B - Method for detecting benzene series pollutants in gas by using internal standard method - Google Patents
Method for detecting benzene series pollutants in gas by using internal standard method Download PDFInfo
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Abstract
The present invention discloses a method for detecting benzene series pollutants in air by using an internal standard method. The method comprises: adopting an absorption tube filled with a benzene series absorption material to absorb and concentrate benzene series pollutants in air or other gases, heating the absorption tube, releasing the absorbed benzene series, carrying out GC-MS system analysis, and using an internal standard method during a benzene series quantitative analysis process, wherein the internal standard substance is added during a work curve drawing process and a sampling analysis process to carry out quantitative analysis on the benzene series. The method has the following advantages that: influence of external factors such as absorption efficiency, desorption efficiency, GC-MS response value drift and the like on the quantitative analysis of the benzene series is reduced, and accuracy of the detection result of the benzene series pollutants in air or other gases is improved.
Description
Technical field
The present invention relates to a kind of method adopting internal standard method to detect the benzo pollutants in gas.
Background technology
Benzene, toluene, dimethylbenzene, ethylbenzene, the benzene homologues such as styrene are indoor air pollutants, are also passenger car internal contamination things.Judge that in room air, passenger car, whether air is qualified, need accurately to detect benzo pollutants.
General testing process: use the benzo pollutants in the adsorption tube absorption of filling absorption benzene homologues material, condensed air or other gas, then heating adsorption pipe, the benzene homologues of release absorption, enters GC-MS systematic analysis, qualitative, quantitative.In testing process, add the accuracy that interior mark can improve detection.Present national standard, international standard and domestic standard to detect in room air, passenger car benzo pollutants in gas, when GC-MS quantitative test, are all adopt external standard method.Can there is drift in the response of GC-MS, detect when external standard method standard working curve is different with sample detection and analyze, the drift of GC-MS response can cause the inaccurate of analysis result.Whether external standard method needs running check working curve to drift about, and just needs again to do standard working curve if there is drift.Process data in GC-MS system, with external standard method work curve time, adopt W
ph~ A
phdependent equation.Such as adopt during linear fit working curve and can obtain following equation:
W
ph＝kA
ph+c
Wherein: W
ph---the quality of detected benzene homologues;
K---the coefficient of linear fit working curve;
A
ph---the detected signal response value of benzene homologues on GC-MS can be area or peak height;
C---the constant obtained of linear fit work song can be 0.
In this equation, even if the benzene homologues of same concentrations, A
phalso passing in time can drift about, thus cause calculating W
phinaccurate.When drifting about serious, need again to do standard working curve.
Adopt sack method to detect benzene in parts, toluene, dimethylbenzene, ethylbenzene, the content of the benzo pollutants such as styrene in automobile industry, also can adopt and add interior calibration method raising detection accuracy.
Particular content can reference paper: volatile organic matter and aldoketones material sampling determination method in HJ/T400-2007 car: ISO16000-6:2011Indoor air-Part6:Determination of volatile organiccompounds in indoor and test hamber air by active sampling on Tenax
sorbent, thermal desorption and gas chromatography using MS or MS-FID (room air-Part VI); Volatile organic compounds-use Tenax in dynamic sampling method measuring cell and in test chamber in gas
adsorbent, thermal desorption, use the gas chromatography of mass spectrum (MS) or mass spectrum-flame ionization detector (MS-FID)).
Summary of the invention
To be solved by this invention be detect room air, benzo pollutants in gas in passenger car, when adopting external standard method GC-MS quantitative test benzene homologues, the response drift of GC-MS causes the inaccurate problem of analysis result.
In order to solve the problem, the invention provides the detection method that a kind of internal standard method detects the benzo pollutants in gas, it is characterized in that, concrete steps are as follows:
Step 1): with complete deuterated benzene (benzene-d6, CAS2037-26-5), full deuterated toluene (toluene-d8, CAS218-009-5), complete deuterated o-xylene (o-xylene-d10, CAS56004-61-6), complete deuterated ethylbenzene (ethylbenzene-d10, CAS25837-05-2), one or more in deuterated styrene (styrene-d8, CAS19361-62-7) and phenyl-monofluoride (CAS207-321-7) are internal standard compound;
Step 2): the preparation of internal standard compound: internal standard compound adopts gas or liquid form, the compound method of the internal standard compound of gas form is: found time by the Teflon sack of sealing, implantation step 1) the internal standard compound liquid of one or more of described internal standard compound, then in this sack, be filled with diluents, place and within 10 ~ 120 minutes, make internal standard compound evaporate in diluents; The compound method of the internal standard compound of liquid form is: measure step 1) the internal standard compound liquid of one or more of described internal standard compound puts into volumetric flask, and use dilution constant volume, shake up;
Step 3): the adsorption tube of production standard working curve sample: after adsorption tube injects benzene homologues calibrating gas/standard solution, implantation step 2 immediately) the internal standard compound gas/solution prepared, take off after purging; In adsorption tube, the quality calculation method of internal standard compound is as follows:
W
is=V
SV
isρ
is／V
W
is---the quality of internal standard compound in adsorption tube;
V
is---be injected into the volume of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
V
s---inject the volume of adsorption tube internal standard compound gas/solution
ρ
is---the density of pure internal standard compound under serviceability temperature condition;
V---be injected into the volume of diluents/solution in the internal standard compound gas/liquid of adsorption tube;
The data creating of multiple adsorption tube is become standard working curve;
Step 4): the adsorption tube making tested sample: add internal standard compound in adsorption tube: under the condition that adsorption tube passes through at 100mL/min nitrogen, inject 1mL step 2) the internal standard compound gas/solution prepared, take off after 1 minute, the sealing of this adsorption tube is preserved, is no more than in 24 hours and uses; With the adsorption tube adding internal standard compound gas, adsorb the gas sample in tested sampling receptacle according to testing requirement; In each adsorption tube, the computing method of the quality of internal standard compound are as follows:
W
is=V
SV
isρ
is／V
W
is---the quality of internal standard compound in adsorption tube;
V
is---be injected into the volume of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
V
s---inject the volume of adsorption tube internal standard compound gas/solution
ρ
is---the density of pure internal standard compound under serviceability temperature condition;
V---be injected into the volume of diluents/solution in the internal standard compound gas/liquid of adsorption tube;
Or internal standard compound is added in sampling receptacle: sample is put into container, accurately be filled with diluents, to reinject step 2) one or more internal standard compound liquid of preparing, 50-80 DEG C of baking 60 ~ 180 minutes, extract the gas sample in tested sampling receptacle by adsorption tube; In adsorption tube, the computing method of internal standard compound quality are as follows:
W
is=V
tV
isρ
is／V
W
is---the quality of internal standard compound in adsorption tube;
V
is---be injected into the volume of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
V
t---adsorption tube extracts the gas volume in tested sampling receptacle;
ρ
is---the density of pure internal standard compound under serviceability temperature condition;
V---be injected into the volume of diluents/solution in the internal standard compound gas/liquid of adsorption tube;
Step 5) detect: use the adsorption tube of GC-MS metric works sample, the adsorption tube of tested sample according to the testing conditions of regulation, choose internal standard compound, the peak area being detected the characteristic ion of benzene homologues or peak height A, use internal standard method to make working curve; According to internal standard method, calculate the benzene homologues amount in adsorption tube according to the peak area of tested benzene homologues or peak height; In GC-MS system, process data, when making working curve, adopt W
ph~ A
ph(W
is/ A
is) fit approach obtains the equation of working curve;
Wherein: W
ph---the quality of tested benzene homologues;
A
ph---the peak area of tested benzene homologues or peak height;
W
is---be injected into the quality of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
A
isthe peak area of the characteristic ion of detected benzene homologues or peak height.
Preferably, described step 2) with step 4) in diluents be purity be 99.999% nitrogen or helium; Dilution is chromatographically pure methyl alcohol.
Preferably, described adsorption tube is TENAX adsorption tube.
Preferably, described step 5) in the testing conditions of GC-MS use HJ/T400-2007, ISO16000-6:2011 defined terms.
Preferably, described step 5) in GC-MS system, process data, when making working curve, adopt W
ph~ A
ph(W
is/ A
is) linear fit or conic fitting mode obtain the equation of working curve.
Further, described step 5) in GC-MS system, process data, when making working curve, adopt W
ph~ A
ph(W
is/ A
is) linear fit mode obtains following equation:
W
ph＝k
isA
ph(W
is/A
is)+c
is
Wherein: W
ph---the quality of detected benzene homologues;
K
is---the coefficient of linear fit working curve;
A
ph---the detected signal response value of benzene homologues on GC-MS, peak height or area;
W
is---add the quality of internal standard compound;
A
is---add the signal response value of internal standard compound on GC-MS, peak height or area;
C
is---the constant obtained of linear fit working curve can be 0.
Compared with external standard method, the advantage of internal standard method is: internal standard method eliminates the error caused by change of GC-MS analog value and operating conditions etc. to a certain extent, and the result of mensuration is comparatively accurate.The error that the change that internal standard method can eliminate the response caused due to the instability of equipment own brings, and the error that the desorption efficiency of adsorption tube is brought.
Embodiment
For making the present invention become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1
In passenger car, the detection of benzo pollutants in air or other gas, uses phenyl-monofluoride to be interior mark.With reference to the method using HJ/T400-2007 standard to specify.
Working curve:
Phenyl-monofluoride is formulated as the methanol solution of 100ug/mL: measure V with micro syringe
is=9.76uL phenyl-monofluoride, injects V
sin the volumetric flask of=100mL, add Chromatographic Pure Methanol to scale, shake up.The density of phenyl-monofluoride is ρ
is=1.024g/cm
3; So quality W of phenyl-monofluoride in this solution of 1uL
isfor:
W
is=V
SV
isρ
is／V
=(1×10
-3mL)×(1.024g/cm
3)×(9.76x10
-3mL)／(100mL)
=1×10
-7g
=100ng
W
is---the quality of internal standard compound in adsorption tube;
V
is---be injected into the volume of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
V
s---inject the volume of adsorption tube internal standard compound gas/solution
ρ
is---the density of pure internal standard compound under serviceability temperature condition;
V---enter the volume of diluents/solution to the internal standard compound gas/liquid of adsorption tube;
Working curve is made at methanol solution with the toluene of 10,100,1000ug/mL:
Blank TENAX adsorption tube installs on standard pipe producing device, high pure nitrogen is passed through with 50mL/min, first inject the phenyl-monofluoride methanol solution of the 100ug/mL of 1uL with microsyringe, the solution of toluene in methyl alcohol of the certain volume that reinjects, makes the toluene of often pipe be following Graded amounts:
Table 1
| 1 | 2 | 3 | 4 | 5 | |
| Phenyl-monofluoride (ng/ pipe) | 100 | 100 | 100 | 100 | 100 |
| Toluene (ng/ pipe) | 10 | 20 | 100 | 200 | 1000 |
The chromatographic condition specified according to HJ/T400-2007 standard is analyzed above-mentioned serial adsorption tube sample introduction.The equipment used is MAKERS TD100, Agilent 7890A/5975C.In data handling procedure, adopt linear fit, mark option in selecting, phenyl-monofluoride is interior mark, and toluene quota ion selects 91, and phenyl-monofluoride quota ion selects 96, uses the peak area of toluene and phenyl-monofluoride to carry out matching, obtains linear work curvilinear equation, R=0.9998
The making of sampling adsorption tube:
Blank TENAX adsorption tube installs on standard pipe producing device, with 50mL/min by high pure nitrogen, injects the phenyl-monofluoride methanol solution of the 100ug/mL of 1uL with microsyringe, continues purging one minute, as sampling adsorption tube.
Sampling process:
Detected passenger car reaches HJ/T400-2007 defined terms, samples 5 simultaneously, be numbered 1#, 2#, 3#, 4#, 5# with the sampling adsorption tube of above-mentioned making, prepares to analyze after sealing.
Toluene level is analyzed: the condition analyzed according to toluene working curve, and analyzed by 5 adsorption tube sample introductions, on the spectrogram obtained, the working curve of the above-mentioned internal standard method of the use of toluene is quantitative; Simultaneously to the working curve quantitative test of the external standard method that spectrogram adopts HJ/T400-2007 to specify.Calculate the content of toluene in gas in passenger car.
Table 2 (unit: mg/m
3)
| 1# | 2# | 3# | 4# | 5# | Mean value | Standard deviation | |
| Internal standard method result | 2.11 | 2.13 | 2.07 | 2.20 | 2.03 | 2.11 | 0.06 |
| External standard method result | 2.22 | 2.01 | 1.97 | 2.24 | 2.17 | 2.12 | 0.12 |
Internal standard method is with external standard method testing result, and toluene level is close, but the standard deviation of internal standard method is less, illustrates that internal standard method testing result is more accurate.
Embodiment 2
Sack method is with deuterated benzene, and deuterated toluene, deuterated o-xylene, deuterated ethylbenzene, deuterated styrene is that internal standard compound detects benzene, toluene, dimethylbenzene, ethylbenzene and cinnamic content in auto parts and components.
Interior gas body: the Teflon sack of sealing 10L, finds time, injects the deuterated benzene of liquid of 5 microlitres successively, liquid deuterated toluene, the deuterated o-xylene liquid of liquid, the deuterated ethylbenzene of liquid and the deuterated styrene of liquid.Sack is accurately filled with 99.999% nitrogen of 5L, places and internal standard compound is evaporate in nitrogen in 30 minutes.
Working curve:
National standard solution GSB07-1986-2005 is adopted to make working curve.National standard solution GSB07-1986-2005 solvent is methyl alcohol, benzene, toluene, ortho-xylene, m-dimethylbenzene, p-dimethylbenzene, and ethylbenzene and cinnamic content are 10,100,1000ug/mL.
Blank TENAX adsorption tube installs on standard pipe producing device, and with 50mL/min by high pure nitrogen, first inject the national standard solution of certain volume, the interior gas body of the 1mL that reinjects, is made the serial adsorption tube containing, for example lower quality:
Table 3
| 1 | 2 | 3 | 4 | 5 | |
| Benzene (ng/ pipe) | 10 | 20 | 100 | 200 | 1000 |
| Deuterated benzene (1x10 -9L/ manages) | 1 | 1 | 1 | 1 | 1 |
| Toluene (ng/ pipe) | 10 | 20 | 100 | 200 | 1000 |
| Deuterated toluene (1x10 -9L/ manages) | 1 | 1 | 1 | 1 | 1 |
| O-xylene (ng/ pipe) | 10 | 20 | 100 | 200 | 1000 |
| M-xylene (ng/ pipe) | 10 | 20 | 100 | 200 | 1000 |
| P-xylene (ng/ pipe) | 10 | 20 | 100 | 200 | 1000 |
| Deuterated o-xylene (1xi0 -9L/ manages) | 1 | 1 | 1 | 1 | 1 |
| Ethylbenzene (ng/ pipe) | 10 | 20 | 100 | 200 | 1000 |
| Deuterated ethylbenzene (1x10 -9L/ manages) | 1 | 1 | 1 | 1 | 1 |
| Styrene (ng/ pipe) | 10 | 20 | 100 | 200 | 1000 |
| Deuterated styrene (1x10 -9L/ manages) | 1 | 1 | 1 | 1 | 1 |
The making of sampling adsorption tube:
Blank TENAX adsorption tube installs on standard pipe producing device, leads to high pure nitrogen with 50mL/min, injects gas body in 1mL, purge one minute with microsyringe, as sampling adsorption tube.
Sample handling processes and sampling:
Automobile instrument panel assembly (IP) puts into the TEDLAR bag that volume is 2000L, is filled with nitrogen 500 liters, then extracts out, repeats twice.Sack is quantitatively filled with 1600L nitrogen again, and the baking oven putting into 65 DEG C deposits 2 hours.After time arrives, simultaneously with two TENAX adsorption tube samplings, sampling condition is, 200mL/min, and acquisition time is 15 minutes, and acquired volume is 3 liters.Two adsorption tubes are labeled as 1# and 2#.
Benzene homologues content analysis:
The chromatographic condition specified according to HJ/T400-2007 standard is analyzed above-mentioned working curve adsorption tube sample introduction.The equipment used is MAKERS TD100, Agilent 7890A/5975C.In data handling procedure, adopt linear fit, interior mark and benzene homologues all use peak area, mark option in selecting.Adopt interior mark: benzene (quota ion 78) with deuterated benzene (quota ion 84) for interior mark; Toluene (quota ion 91) with deuterated toluene (quota ion 98) for interior mark; O-xylene (quota ion 91), m-xylene (quota ion 91) P-xylene (quota ion 91) with deuterated o-xylene (quota ion 98) for interior mark; Ethylbenzene (quota ion 91) with deuterated ethylbenzene (quota ion 98) for interior mark; Styrene (quota ion 104) with deuterated styrene (quota ion 112) for interior mark.
Machine analysis gone up immediately by 1# pipe.2# pipe room temperature lower seal is preserved, and goes up machine analysis again after 24 hours.According to the peak area of benzene homologues in the spectrogram of 1# and 2#, quantitative with the working curve of above-mentioned internal standard method; In addition, adopt the working curve of external standard method quantitative to spectrogram.
Testing result:
Table 4
| 1# (interior mark) | 1# (external standard) | 2# (interior mark) | 2# (external standard) | |
| Benzene (ng/ pipe) | Do not detect | Do not detect | Do not detect | Do not detect |
| Toluene (ng/ pipe) | 131 | 120 | 125 | 143 |
| Neighbour, P-xylene (ng/ pipe) | 220 | 210 | 209 | 248 |
| Ethylbenzene (ng/ pipe) | 89 | 92 | 93 | 109 |
| Styrene (ng/ pipe) | 62 | 68 | 65 | 71 |
Testing result and the external standard method of his-and-hers watches 4 ask extreme difference and relative extreme difference respectively, the results are shown in following table:
Table 5
Very close with the result of external standard method from the testing result internal standard method of table 4-5,1#; The testing result of 2#, except benzene does not detect, other several benzene homologues are all that external standard method result is apparently higher than internal standard method testing result.From table 5,1#, 2# internal standard method result difference is basic within 5%; 1#, 2# external standard method result difference is basic 10 ~ 18%.This is because twice assay intervals 24 hours, the response of GC-MS to benzene homologues there occurs drift, causes the results change of external standard method.Therefore, internal standard method result is more stable than external standard method.
Claims (6)
1. internal standard method detects a detection method for the benzo pollutants in gas, and it is characterized in that, concrete steps are as follows:
Step 1): with complete deuterated benzene, full deuterated toluene, complete deuterated o-xylene, complete deuterated ethylbenzene, one or more in deuterated styrene and phenyl-monofluoride are internal standard compound;
Wherein, complete deuterated benzene is expressed as benzene-d6, CAS 2037-26-5; Full deuterated toluene is expressed as toluene-d8, CAS 218-009-5; Complete deuterated o-xylene is expressed as o-xylene-d10, CAS 56004-61-6; Complete deuterated ethylbenzene is expressed as ethylbenzene-d10, CAS 25837-05-2; Deuterated styrene is expressed as styrene-d8, CAS 19361-62-7; Phenyl-monofluoride is expressed as CAS 207-321-7;
Step 2): the preparation of internal standard compound: internal standard compound adopts gas or liquid form, the compound method of the internal standard compound of gas form is: found time by the Teflon sack of sealing, implantation step 1) the internal standard compound liquid of one or more of described internal standard compound, then in this sack, be filled with diluents, place and within 10 ~ 120 minutes, make internal standard compound evaporate in diluents; The compound method of the internal standard compound of liquid form for: the internal standard compound liquid measuring one or more of internal standard compound described in step 1) puts into volumetric flask, uses dilution constant volume, shakes up;
Step 3): the adsorption tube of production standard working prototype: after adsorption tube injects benzene homologues calibrating gas/standard solution, implantation step 2 immediately) the internal standard compound gas/solution prepared, take off after purging; In adsorption tube, the quality calculation method of internal standard compound is as follows:
W
is=V
SV
isρ
is/ V
W
is---the quality of internal standard compound in adsorption tube;
V
is---be injected into the volume of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
V
s---inject the volume of adsorption tube internal standard compound gas/solution
ρ
is---the density of pure internal standard compound under serviceability temperature condition;
V---be injected into the volume of diluents/solution in the internal standard compound gas/liquid of adsorption tube;
The data creating of multiple adsorption tube is become standard working curve;
Step 4): the adsorption tube making tested sample: add internal standard compound in adsorption tube: under the condition that adsorption tube passes through at 100mL/min nitrogen, inject 1mL step 2) the internal standard compound gas/solution prepared, take off after 1 minute, the sealing of this adsorption tube is preserved, is no more than in 24 hours and uses; With the adsorption tube adding internal standard compound gas, adsorb the gas sample in tested sampling receptacle according to testing requirement; In each adsorption tube, the computing method of the quality of internal standard compound are as follows:
W
is=V
SV
isρ
is/ V
W
is---the quality of internal standard compound in adsorption tube;
V
is---be injected into the volume of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
V
s---inject the volume of adsorption tube internal standard compound gas/solution
ρ
is---the density of pure internal standard compound under serviceability temperature condition;
V---be injected into the volume of diluents/solution in the internal standard compound gas/liquid of adsorption tube;
Or internal standard compound is added in sampling receptacle: sample is put into container, accurately be filled with diluents, to reinject step 2) one or more internal standard compound liquid of preparing, 50-80 DEG C of baking 60 ~ 180 minutes, extract the gas sample in tested sampling receptacle by adsorption tube; In adsorption tube, the computing method of internal standard compound quality are as follows:
W
is=V
tV
isρ
is/ V
W
is---the quality of internal standard compound in adsorption tube;
V
is---be injected into the volume of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
V
t---adsorption tube extracts the gas volume in tested sampling receptacle;
ρ
is---the density of pure internal standard compound under serviceability temperature condition;
V---be injected into the volume of diluents/solution in the internal standard compound gas/liquid of adsorption tube;
Step 5) detects: use the adsorption tube of GC-MS metric works sample, the adsorption tube of tested sample according to the testing conditions of regulation, chooses internal standard compound, the peak area being detected the characteristic ion of benzene homologues or peak height A, uses internal standard method to make working curve; According to internal standard method, calculate the benzene homologues amount in adsorption tube according to the peak area of tested benzene homologues or peak height; In GC-MS system, process data, when making working curve, adopt W
ph~ A
ph(W
is/ A
is) fit approach obtains the equation of working curve;
Wherein: W
ph---the quality of tested benzene homologues;
A
ph---the peak area of tested benzene homologues or peak height;
W
is---be injected into the quality of internal standard compound pure in the internal standard compound gas/liquid of adsorption tube;
A
isthe peak area of the characteristic ion of detected benzene homologues or peak height.
2. internal standard method as claimed in claim 1 detects the detection method of the benzo pollutants in gas, it is characterized in that, described step 2) be purity with the diluents in step 4) be 99.999% nitrogen or helium; Dilution is chromatographically pure methyl alcohol.
3. internal standard method as claimed in claim 1 detects the detection method of the benzo pollutants in gas, and it is characterized in that, described adsorption tube is TENAX adsorption tube.
4. internal standard method as claimed in claim 1 detects the detection method of the benzo pollutants in gas, it is characterized in that, in described step 5), the testing conditions of GC-MS uses HJ/T 400-2007, ISO 16000-6:2011 defined terms.
5. internal standard method as claimed in claim 1 detects the detection method of the benzo pollutants in gas, it is characterized in that, processes data in described step 5) in GC-MS system, when making working curve, adopts W
ph~ A
ph(W
is/ A
is) linear fit or conic fitting mode obtain the equation of working curve.
6. internal standard method as claimed in claim 5 detects the detection method of the benzo pollutants in gas, it is characterized in that, processes data in described step 5) in GC-MS system, when making working curve, adopts W
ph~ A
ph(W
is/ A
is) linear fit mode obtains following equation:
W
ph=
k is A
ph(W
is/A
is) +
c is
Wherein: W
ph---the quality of detected benzene homologues;
k is ---the coefficient of linear fit working curve;
A
ph---detected signal response value, peak height or the area of benzene homologues on GC-MS;
W
is---add the quality of internal standard compound;
A
is---add signal response value, peak height or the area of internal standard compound on GC-MS;
c is ---the constant obtained of linear fit working curve is 0.
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| CN105044242A (en) * | 2015-08-28 | 2015-11-11 | 保护伞环保科技成都有限公司 | Method for determining styrene content of indoor air after decoration |
| CN105259014B (en) * | 2015-11-04 | 2019-01-01 | 中国汽车技术研究中心 | A kind of measurement method of VOCs solution and the preparation method of calibrating gas |
| CN106631649B (en) * | 2016-12-01 | 2020-02-18 | 深圳大学 | Method for preparing deuterated chemical and deuterated chemical |
| CN106950303B (en) * | 2017-03-21 | 2020-01-21 | 山西医科大学 | Method for measuring benzene series in biological sample blood |
| CN109781896B (en) * | 2019-03-07 | 2022-06-17 | 西北大学 | Standard series and gas sample analysis method based on internal standard method |
| CN112462000A (en) * | 2020-11-17 | 2021-03-09 | 广东电网有限责任公司电力科学研究院 | Gas mixing device for internal standard method |
| CN112345682B (en) * | 2020-11-23 | 2023-06-30 | 中国第一汽车股份有限公司 | Detection method for benzene volatile organic components and application thereof |
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