CN108956810A - The detection method of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas - Google Patents
The detection method of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas Download PDFInfo
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Abstract
The present invention provides a kind of detection methods of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas, comprising: is detected using gas chromatograph-mass spectrometer (GC-MS) to perfluor isobutyronitrile mixed gas to be measured, obtains foreign gas ingredient and discreet volume score；According to discreet volume score, configuration standard gas；Calibrating gas is detected using gas chromatograph or the gas chromatograph-mass spectrometer (GC-MS), the standard curve and its fit equation of foreign gas are obtained using external standard method；Perfluor isobutyronitrile mixed gas to be measured is detected again, obtains the volume fraction of every kind of foreign gas described in the perfluor isobutyronitrile mixed gas to be measured using fit equation；Volume fraction based on foreign gas obtains the purity of perfluor isobutyronitrile in the mixed gas to be measured.The invention proposes a kind of new methods of perfluor isobutyronitrile purity in detection perfluor isobutyronitrile mixed gas, and detection is accurate and reliable, easy to operate, convenience of calculation.
Description
Technical field
The present invention relates to product testing analysis fields, in particular to perfluor in a kind of perfluor isobutyronitrile mixed gas
The detection method of isobutyronitrile purity.
Background technique
Sulfur hexafluoride (SF6) gas is widely used in high voltage installation as good insulation and arc-extinguishing medium, however six
The global warming coefficient (GWP) of sulfur fluoride is 23900 times of CO2, and therefore, power industry needs the substitution using sulfur hexafluoride
Product.The mix insulation gas of perfluor isobutyronitrile (C4F7N) and CO2 composition substitutes gas as the novel sulfur hexafluoride of electrical equipment
Body has been used for the electrical equipments such as 145kV gas-insulated switchgear (GIS) and 420kV gas-insulated transmission line (GIL).
The GWP of perfluor isobutyronitrile is only the 10% of SF6, and condensing temperature is -4.7 DEG C, is mixed with buffer gas such as CO2, N2, comprehensive performance
Equipment requirement can be met, and GWP is down to the 2% of sulfur hexafluoride.As it can be seen that perfluor isobutyronitrile gas has extensively in power industry
Wealthy application prospect, the detection method for establishing perfluor isobutyronitrile gas are of crucial importance.
GB/T 12022 " industrial sulfur hexafluoride " defines the requirement of industrial sulfur hexafluoride, such as: the quality of sulfur hexafluoride point
Number is not less than 99.9%, and the mass fraction of air, carbon tetrafluoride is not higher than 0.04% in sulfur hexafluoride, and the mass fraction of moisture is not
Higher than 0.0005%.With reference to the performance indicator of 12022 pairs of GB/T industrial sulfur hexafluorides, perfluor isobutyronitrile gas is applied to electrical
When equipment, the purity of perfluor isobutyronitrile in perfluor isobutyronitrile mixed gas should be controlled, to guarantee the quality of the mixed gas.Cause
This, needs to establish the detection side of the impurity such as the purity of perfluor isobutyronitrile and air, fluoro-gas in perfluor isobutyronitrile mixed gas
Method.
Summary of the invention
In consideration of it, the invention proposes a kind of detection method of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas,
Aim to solve the problem that the problem of perfluor isobutyronitrile purity and impurity component detect in perfluor isobutyronitrile mixed gas.
The embodiment of the invention provides a kind of detection methods of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas, should
Method includes:
Step S1 detects perfluor isobutyronitrile mixed gas to be measured using gas chromatograph-mass spectrometer (GC-MS), according to institute
Characteristic mass-charge of every kind of gas is obtained than determining perfluor isobutyronitrile and every kind of impurity gas in perfluor isobutyronitrile mixed gas to be measured
The ingredient of body obtains the discreet volume point of perfluor isobutyronitrile and every kind of foreign gas according to the chromatographic peak area of every kind of gas of gained
Number；
Step S2 is every kind of foreign gas configuration at least three according to the ingredient and discreet volume score of every kind of foreign gas
The different calibrating gas of kind foreign gas volume fraction, calibrating gas is by same foreign gas to be measured and background gas group
At；
Step S3 detects calibrating gas using gas chromatograph or gas chromatograph-mass spectrometer (GC-MS), obtains standard
The chromatographic peak area of gas is chromatographic peak area and standard gas volume score of the every kind of foreign gas based on calibrating gas, builds
Day-mark directrix curve and its corresponding fit equation；
Step S4, using gas chromatograph or gas chromatograph-mass spectrometer (GC-MS) to perfluor isobutyronitrile mixed gas to be measured into
Row detection, obtains the chromatographic peak area of perfluor isobutyronitrile and every kind of foreign gas, passes through the chromatographic peak area of every kind of foreign gas
The volume fraction of every kind of foreign gas in perfluor isobutyronitrile mixed gas to be measured is obtained by fit equation；
Step S5 is calculated in perfluor isobutyronitrile mixed gas to be measured complete based on the volume fraction of every kind of foreign gas
The purity of fluorine isobutyronitrile.
Specifically, the chromatographic column of gas chromatograph-mass spectrometer (GC-MS) comprises at least one of the following: Rtx-200 chromatographic column, GS-
GasPro chromatographic column；
The chromatographic column of gas chromatograph comprises at least one of the following: Rtx-200 chromatographic column, GS-GasPro chromatographic column,
Porapak Q chromatographic column.
Specifically, step S1 includes:
Step S11 detects perfluor isobutyronitrile mixed gas to be measured using gas chromatography-mass spectrometry instrument, obtains every
Characteristic mass-charge ratio of kind gas, is compared according to the characteristic mass of every kind of gas-charge ratio with NIST database, really
The ingredient of perfluor isobutyronitrile and every kind of foreign gas in fixed perfluor isobutyronitrile mixed gas to be measured；
Step S12 calculates every kind of foreign gas according to following formula (1) according to the chromatographic peak area of every kind of gas of gained
Discreet volume score:
Wherein, AiAnd CiThe chromatographic peak area and volume fraction of respectively i-th kind gas.
Specifically, fit equation is following formula (2), the volume fraction C of every kind of foreign gasziAccording to following formula (2)
It is calculated:
Czi=ai×Azi+bi (2)
Wherein, AziFor the chromatographic peak area of i-th kind of foreign gas, aiAnd biFor the fitting coefficient of standard curve.
Specifically, step S5 includes:
Step S51 calculates the body of perfluor isobutyronitrile according to following formula (3) based on the volume fraction of every kind of foreign gas
Fraction CC4F7N:
CC4F7N=1- ∑ Czi (3)
Wherein, CziFor the volume fraction of i-th kind of foreign gas；
Step S52, the volume fraction of volume fraction and perfluor isobutyronitrile based on every kind of foreign gas, according to following formula
(4) the mass fraction r of every kind of foreign gas is calculatedzi:
Wherein, MziFor the relative molecular mass of i-th kind of foreign gas；
Step S53 calculates the pure of perfluor isobutyronitrile according to following formula (5) based on the mass fraction of every kind of foreign gas
Spend rC4F7N
rC4F7N=1- ∑ rzi (5)。
Specifically, the volume fraction of every kind of foreign gas is identical as the order of magnitude of discreet volume score in calibrating gas.
Specifically, the item that gas chromatography-mass spectrometry instrument detects perfluor isobutyronitrile mixed gas to be measured in step S1
Part are as follows: use split sampling mode, split ratio 50: 1, prime temperature is 230 DEG C, and ion source temperature is 250 DEG C, and temperature program is
Until 200 DEG C of holding 5min, chromatographic column are Rtx-200 chromatographic column, flow rate of carrier gas is by 35 DEG C of holdings 15min, 10 DEG C/min
1.0mL/min, nebulizer gas pressure 0.5MPa；Wherein, Rtx-200 chromatogram column length is 105m, internal diameter 0.32mm, and film thickness is
1.50μm。
Specifically, in step S3 using gas chromatograph or gas chromatography-mass spectrometry instrument to calibrating gas carry out detection and
The item that perfluor isobutyronitrile mixed gas to be measured is detected using gas chromatograph or gas chromatography-mass spectrometry instrument in step S4
Part is equal are as follows: split sampling mode, split ratio 5: 1 are used, TCD temperature is 150 DEG C, and temperature program is 200 DEG C of holding 10min,
Chromatographic column is Porapak Q chromatographic column, flow rate of carrier gas 44mL/min, nebulizer gas pressure 0.5MPa；Wherein, Porapak Q chromatographic column
For 80/100 mesh, a length of 6 feet, internal diameter 2mm.
Specifically, foreign gas comprises at least one of the following: air, hexafluoropropene.
Specifically, background gas is helium.
The detection method of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas provided in an embodiment of the present invention, by every
Characteristic mass-charge ratio of kind gas, can determine the impurity component in perfluor isobutyronitrile mixed gas to be measured, realize to this
The qualitative analysis of mixed gas to be measured；The discreet volume point of foreign gas is obtained by the chromatographic peak area of every kind of gas simultaneously
Number, and it is based on the discreet volume score, the relationship of foreign gas volume fraction and concentration is obtained using external standard method, to be mixed
Close gas in perfluor isobutyronitrile purity, propose it is a kind of detection perfluor isobutyronitrile mixed gas in perfluor isobutyronitrile purity it is new
Method, detection is accurate and reliable, easy to operate, convenience of calculation, is suitable for a large amount of perfluor isobutyronitrile mixed gas samples to be tested.
Detailed description of the invention
Fig. 1 is the example of the detection method of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas in the embodiment of the present invention
Property flow chart；
Fig. 2 is that gas chromatograph or gas chromatograph-mass spectrometer (GC-MS) carry out gaseous sample detection in the embodiment of the present invention
Flow diagram；
Fig. 3 estimates chromatogram for perfluor isobutyronitrile mixed gas to be measured in the embodiment of the present invention；
Fig. 4 is the mass spectrogram of perfluor isobutyronitrile in perfluor isobutyronitrile mixed gas to be measured in the embodiment of the present invention；
Fig. 5 is the mass spectrogram of air in perfluor isobutyronitrile mixed gas to be measured in the embodiment of the present invention；
Fig. 6 is the mass spectrogram of hexafluoropropene in perfluor isobutyronitrile mixed gas to be measured in the embodiment of the present invention；
Fig. 7 is the canonical plotting that air (indicates) chromatographic peak area and volume fraction with nitrogen in the embodiment of the present invention；
Fig. 8 is the canonical plotting of hexafluoropropene chromatographic peak area and volume fraction in the embodiment of the present invention；
Fig. 9 is the detection chromatogram again of perfluor isobutyronitrile mixed gas to be measured in the embodiment of the present invention.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvement and modification are also considered as
Protection scope of the present invention.
It is accurate to realize in the mixed gas in perfluor isobutyronitrile mixed gas, usual foreign gas content is less
Perfluor isobutyronitrile and foreign gas qualitative and quantitative detection, it is particularly significant for the quality for evaluating the mixed gas.Based on this, this reality
It applies example and provides a kind of detection method of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas.
Fig. 1 shows the detection side of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas according to an embodiment of the present invention
The exemplary process diagram of method.
As shown in Figure 1, the detection method includes:
Step S1 detects perfluor isobutyronitrile mixed gas to be measured using gas chromatograph-mass spectrometer (GC-MS), according to institute
Characteristic mass-charge of every kind of gas is obtained than determining perfluor isobutyronitrile and every kind of impurity gas in perfluor isobutyronitrile mixed gas to be measured
The ingredient of body obtains the discreet volume point of perfluor isobutyronitrile and every kind of foreign gas according to the chromatographic peak area of every kind of gas of gained
Number；
Step S2 is every kind of foreign gas configuration at least three according to the ingredient and discreet volume score of every kind of foreign gas
The different calibrating gas of kind foreign gas volume fraction, calibrating gas is by same foreign gas to be measured and background gas group
At；
Step S3 detects calibrating gas using gas chromatograph or gas chromatograph-mass spectrometer (GC-MS), obtains standard
The chromatographic peak area of gas is chromatographic peak area and standard gas volume score of the every kind of foreign gas based on calibrating gas, builds
Day-mark directrix curve and its corresponding fit equation；
Step S4, using gas chromatograph or gas chromatograph-mass spectrometer (GC-MS) to perfluor isobutyronitrile mixed gas to be measured into
Row detection, obtains the chromatographic peak area of perfluor isobutyronitrile and every kind of foreign gas, passes through the chromatographic peak area of every kind of foreign gas
The volume fraction of every kind of foreign gas in perfluor isobutyronitrile mixed gas to be measured is obtained by fit equation；
Step S5 is calculated in perfluor isobutyronitrile mixed gas to be measured complete based on the volume fraction of every kind of foreign gas
The purity of fluorine isobutyronitrile.
In the embodiment of the present invention, foreign gas can with air, hexafluoropropene, carbon tetrafluoride, carbon dioxide etc. any one
Or it is a variety of.Firstly, perfluor isobutyronitrile mixed gas to be measured is detected by gas chromatograph-mass spectrometer (GC-MS), according to every kind obtained
The characteristic mass of gas-charge ratio can obtain gaseous mixture to be measured using comparing with standard database or the modes such as analytic derivation
Every kind of gas componant in body realizes the qualitative analysis to foreign gas, while can be according to the chromatographic peak area of every kind of gas
Obtain the discreet volume score of every kind of gas；It, can be with configuration standard later according to the ingredient of foreign gas and discreet volume score
Gas, the calibrating gas are made of same foreign gas and background gas, can configure at least three for every kind of foreign gas
Kind have different impurities gas volume fraction calibrating gas, wherein background gas can be helium, be also possible to argon gas etc. its
His inert gas；External standard method can be used, it is every to what is configured using gas chromatograph or the gas chromatograph-mass spectrometer (GC-MS)
Every kind of calibrating gas sequentially determining of kind foreign gas, can be according to the chromatographic peak of every kind of calibrating gas for every kind of foreign gas
Area and volume fraction establish standard curve, and obtain corresponding fit equation according to the curve, and wherein the fit equation can be with
For y=ax+b, it is also possible to other equations being consistent with standard curve；Gas chromatograph or the gas phase color are utilized again
Spectrum-mass spectrometer detects the mixed gas to be measured, obtains the chromatographic peak area of every kind of gas, can be with every kind of impurity gas
The chromatographic peak area of body substitutes into fit equation and is calculated, and obtains the accurate volume of every kind of foreign gas point in mixed gas to be measured
Number, calculates to obtain the accurate purity of perfluor isobutyronitrile in mixed gas based on the accurate volume fraction of every kind of foreign gas.It needs
It is noted that detect again mixed gas to be measured instrument and condition it is identical as the instrument of examination criteria gas and condition needs,
It just can guarantee the accuracy and reliability of external standard method.
In above-described embodiment, by first using preestimating method to estimate the ingredient and volume of perfluor isobutyronitrile mixed gas to be detected
Score uses external standard method further according to the result estimated, the standard curve of foreign gas is obtained, according to the mixing to be measured detected again
The chromatographic peak area of gaseous impurity gas obtains the volume fraction of accurate foreign gas using the standard curve, to obtain
The purity of perfluor isobutyronitrile in mixed gas solves different there has been no perfluor in mixed gas is accurately and reliably calculated in the prior art
The technical issues of purity of butyronitrile, detection is accurate and reliable, easy to operate, convenience of calculation, is suitable for a large amount of perfluor isobutyronitriles and mixes
Gas sample to be tested.
Further, the chromatographic column of gas chromatograph-mass spectrometer (GC-MS) comprises at least one of the following: Rtx-200 chromatographic column,
GS-GasPro chromatographic column；
The chromatographic column of gas chromatograph comprises at least one of the following: Rtx-200 chromatographic column, GS-GasPro chromatographic column,
Porapak Q chromatographic column.
In the embodiment of the present invention, gas chromatograph-mass spectrometer (GC-MS) can select Rtx-200 chromatographic column, can also select GS-
GasPro chromatographic column；Gas chromatograph can select Rtx-200 chromatographic column, can also select GS-GasPro chromatographic column, can be with
Select Porapak Q chromatographic column, by selecting suitable chromatographic column, may be implemented foreign gas type it is more when every kind of gas compared with
Good separating effect.
In more embodiments, gas chromatograph-mass spectrometer (GC-MS) or gas chromatograph can select other kinds of capillary
Pipe chromatographic column, chromatography column etc. can be selected according to specific requirements, as long as every kind of gas in mixed gas may be implemented
Separation.
Further, step S1 includes:
Step S11 detects perfluor isobutyronitrile mixed gas to be measured using gas chromatography-mass spectrometry instrument, obtains every
Characteristic mass-charge ratio of kind gas, is compared according to the characteristic mass of every kind of gas-charge ratio with NIST database, really
The ingredient of perfluor isobutyronitrile and every kind of foreign gas in fixed perfluor isobutyronitrile mixed gas to be measured；
Step S12 calculates every kind of foreign gas according to following formula (1) according to the chromatographic peak area of every kind of gas of gained
Discreet volume score:
Wherein, AiAnd CiThe chromatographic peak area and volume fraction of respectively i-th kind gas.
In the embodiment of the present invention, it can be compared according to every kind of gas characteristic mass-charge ratio with NIST database, really
The ingredient of fixed every kind of gas can quick and precisely carry out ingredient and determine in the case where more than foreign gas type.
Further, fit equation is following formula (2), the volume fraction C of every kind of foreign gasziAccording to following formula
(2) it is calculated:
Czi=ai×Azi+bi (2)
Wherein, AaFor the chromatographic peak area of i-th kind of foreign gas, aiAnd biFor the fitting coefficient of standard curve.
In the embodiment of the present invention, it can be fitted to obtain the corresponding equation of standard curve using linear linear function, wherein quasi-
Collaboration number aiIt can be non-zero any number, fitting coefficient biIt can be any number, including can be 0.For every kind of impurity gas
Body can establish coordinate system according to the volume fraction of the calibrating gas of different volumes score and the value of chromatographic peak area, draw mark
The point of directrix curve is fitted each point using Data Analysis Software or other modes, obtains corresponding standard curve and intends
It closes equation formulations (2), to obtain the linear relationship of every kind of foreign gas volume fraction and chromatographic peak area.
Further, step S5 includes:
Step S51 calculates the body of perfluor isobutyronitrile according to following formula (3) based on the volume fraction of every kind of foreign gas
Fraction CC4F7N:
CC4F7N=1- ∑ Czi (3)
Wherein, CziFor the volume fraction of i-th kind of foreign gas；
Step S52, the volume fraction of volume fraction and perfluor isobutyronitrile based on every kind of foreign gas, according to following formula
(4) the mass fraction r of every kind of foreign gas is calculatedzi:
Wherein, MziFor the relative molecular mass of i-th kind of foreign gas；
Step S53 calculates the pure of perfluor isobutyronitrile according to following formula (5) based on the mass fraction of every kind of foreign gas
Spend rC4F7N:
rC4F7N=1- ∑ rzi (5)。
Further, the volume fraction of every kind of foreign gas is identical as the order of magnitude of discreet volume score in calibrating gas.
In the embodiment of the present invention, the foreign gas volume fraction of calibrating gas is configurable to estimate body with foreign gas
Fraction same order, to better ensure that the accuracy of quantified by external standard method.
Further, gas chromatography-mass spectrometry instrument detects perfluor isobutyronitrile mixed gas to be measured in step S1
Condition are as follows: use split sampling mode, split ratio 50: 1, prime temperature is 230 DEG C, and ion source temperature is 250 DEG C, temperature program
For 35 DEG C of holdings 15min, 10 DEG C/min until 200 DEG C of holding 5min, chromatographic column are Rtx-200 chromatographic column, flow rate of carrier gas is
1.0mL/min, nebulizer gas pressure 0.5MPa；Wherein, Rtx-200 chromatogram column length is 105m, internal diameter 0.32mm, and film thickness is
1.50μm。
Further, calibrating gas is carried out using gas chromatograph or the gas chromatography-mass spectrometry instrument in step S3
Perfluor isobutyronitrile mixed gas to be measured is examined using gas chromatograph or gas chromatography-mass spectrometry instrument in detection and step S4
The condition of survey is equal are as follows: uses split sampling mode, split ratio 5: 1, TCD temperature is 150 DEG C, and temperature program is 200 DEG C of holdings
10min, chromatographic column are Porapak Q chromatographic column, flow rate of carrier gas 44mL/min, nebulizer gas pressure 0.5MPa；Wherein, Porapak Q
Chromatographic column be 80/100 mesh, a length of 6 feet, internal diameter 2mm.
Further, foreign gas comprises at least one of the following: air, hexafluoropropene.
Further, background gas is helium.
Fig. 2 is that gas chromatograph or gas chromatograph-mass spectrometer (GC-MS) carry out gaseous sample detection in the embodiment of the present invention
Flow diagram.
As shown in Fig. 2, gaseous sample, such as perfluor isobutyronitrile mixed gas to be measured, calibrating gas, when being sampled, gas
Sampling valve 4 is in closed state shown in Fig. 2, and gaseous sample enters analysis gas access 6 from gas flowmeter 3, hence into
Then quantity tube 5 is vented from analysis gas port 7, carrier gas enters gas sampling valve 4 by carrier gas pressure reducing valve 2 in carrier gas steel cylinder 1,
Then detector 9 is reached by chromatographic column 8；When sample detection, gas sampling valve 4 is in the open state, and (Fig. 2 is not shown, gas
1, the 2 of sampling valve 4 are connected, and 3,4 are connected, and 5,6 are connected), after carrier gas enters gas sampling valve 4, by quantity tube 5, by quantity tube 5
In gaseous sample bring chromatographic column 8 into and separated, and the gas after separation is loaded into detector 9 and is detected.Detector 9 can
To be mass detector, it is also possible to TCD detector, the project that specifically can according to need detection is selected.Carrier gas can be with
It is the common carrier such as helium, hydrogen, argon gas.
Embodiment 1
Present embodiments provide a kind of detection method of perfluor isobutyronitrile purity in perfluor isobutyronitrile mixed gas, this method
Include:
Step S1: using analysis condition as shown in Table 1 using gas chromatograph-mass spectrometer (GC-MS) (GC/MS), to be measured complete
Fluorine isobutyronitrile mixed gas is detected, and the mass spectrogram of mixed gas chromatogram to be measured and such as Fig. 4-6 as shown in Figure 3 is obtained.
Table 1GC/MS detects the analysis condition of perfluor isobutyronitrile mixed gas to be measured
From mixed gas chromatogram to be measured shown in Fig. 3 as can be seen that there are three kinds of gases, one of which is main gas
Body, in addition two kinds are foreign gas.Meanwhile characteristic mass-charge ratio in the mass spectrogram of every kind of gas according to shown in Fig. 4-6
(mass-to-charge ratio) is compared with NIST database, can determine that Fig. 4, Fig. 5, Fig. 6 are respectively perfluor isobutyronitrile, air, hexafluoro third
The mass spectrogram of alkene, the ingredient for estimating every kind of gas are listed in the table below 2.
Table 2GC/MS the qualitative analysis
It is calculated according to every kind of gas integrating peak areas value in Fig. 3 using following formula (1) using the gas componant estimated
The discreet volume score of every kind of foreign gas, is listed in the table below 3:
Wherein, AiAnd CiThe chromatographic peak area and volume fraction of respectively i-th kind gas.
Table 3GC/MS detects the peak area and volume fraction of perfluor isobutyronitrile mixed gas to be measured
| Gas type | Integrating peak areas A | Discreet volume score C (%) |
| Air | 145070353 | 0.37 |
| Hexafluoropropene | 96463326 | 0.25 |
| Perfluor isobutyronitrile | 38453691659 | 99.48 |
Step S2: according to the ingredient and discreet volume score of every kind of foreign gas in table 3, (nitrogen table is used for air
Show), hexafluoropropene, three kinds of different calibrating gas of body volume fraction are respectively configured, that is, three kinds of volume fraction differences are respectively configured
Air-helium calibrating gas and the different hexafluoropropene-helium calibrating gas of three kinds of volume fractions, wherein volume fraction model
It encloses for (100~1000) × 10-6。
Step S3: using gas chromatograph (GC) use analysis condition as shown in table 4, to six kinds of calibrating gas successively into
Row detection, obtains the chromatographic peak area of every kind of calibrating gas.
The GC analysis condition of 4 calibrating gas of table
| Analysis condition | Parameter setting |
| Chromatography column parameter | Porapak Q(6m×3mm) |
| Flow rate of carrier gas | 44mL/min |
| Nebulizer gas pressure | 0.5MPa |
| Temperature program | 200 DEG C of holding 10min |
| Quantitative loop volume | 250μL |
| Shunt mode | Split sampling |
| Split ratio | 5∶1 |
| TCD temperature | 150℃ |
According to air (being indicated with nitrogen), the chromatographic peak area and gas volume fraction of hexafluoropropene calibrating gas, respectively
Establish the standard curve of air (being indicated with nitrogen), hexafluoropropene chromatographic peak area and volume fraction, as shown in Figure 7, Figure 8, root
It is fitted to obtain corresponding equation using software according to the standard curve, as shown in table 5.
The standard curve fit equation of 5 foreign gas of table
Step S4: analysis condition as shown in table 4 is used using the GC in above-mentioned steps, perfluor isobutyronitrile to be measured is mixed
Gas is detected again, mixed gas chromatogram to be measured as shown in Figure 9 is obtained, according to the chromatographic peak of air and hexafluoropropene
Area, using standard curve fit equation shown in table 5, the volume fraction for obtaining air and hexafluoropropene is respectively 0.05% He
0.004%.
Step S5: it according to the volume fraction of above-mentioned air and hexafluoropropene, is counted respectively according to following formula (3), (4), (5)
Calculate the volume fraction C of perfluor isobutyronitrileC4F7N, the air and hexafluoropropene mass fraction rzi, perfluor isobutyronitrile purity
rC4F7N, it is listed in table 6:
CC4F7N=1- ∑ Czi (3)
Wherein, CziFor the volume fraction of i-th kind of foreign gas；
Wherein, MziFor the relative molecular mass of i-th kind of foreign gas；
rC4F7N=1- ∑ rzi (5)。
Table 6GC/MS detects C4F7The volume fraction and mass fraction of N
| Gas type | Volume fraction r (%) | Mass fraction r (%) |
| Air | 0.05 | 0.007 |
| Hexafluoropropene | 0.004 | 0.003 |
| Perfluor isobutyronitrile | 99.95 | 99.99 |
The embodiment of the present invention carries out qualitative analysis by first estimating detection to perfluor isobutyronitrile mixed gas to be measured, then base
In estimating numerical value, the standard curve of foreign gas is further obtained by external standard method, is counted for accurate according to testing result
The content for calculating foreign gas and perfluor isobutyronitrile realizes perfluor isobutyronitrile in accurate and reliable calculating perfluor isobutyronitrile mixed gas
The effect of purity, easy to operate, convenience of calculation.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. the detection method of perfluor isobutyronitrile purity in a kind of perfluor isobutyronitrile mixed gas, which is characterized in that the method packet
It includes:
Step S1 detects perfluor isobutyronitrile mixed gas to be measured using gas chromatograph-mass spectrometer (GC-MS), every according to gained
Characteristic mass-charge of kind gas is than determining perfluor isobutyronitrile and every kind of impurity gas in the perfluor isobutyronitrile mixed gas to be measured
The ingredient of body obtains the pre- of the perfluor isobutyronitrile and every kind of foreign gas according to the chromatographic peak area of every kind of gas of gained
Estimate volume fraction；
Step S2, according to the ingredient of foreign gas described in every kind and discreet volume score, for every kind of foreign gas configure to
The different calibrating gas of few three kinds of foreign gas volume fractions, the calibrating gas by the same foreign gas to be measured and
Background gas composition；
Step S3 detects the calibrating gas using gas chromatograph or the gas chromatograph-mass spectrometer (GC-MS), obtains
The chromatographic peak area of the calibrating gas is chromatographic peak area of the every kind of foreign gas based on the calibrating gas and described
Standard gas volume score establishes standard curve and its corresponding fit equation；
Step S4, it is mixed to the perfluor isobutyronitrile to be measured using the gas chromatograph or the gas chromatograph-mass spectrometer (GC-MS)
It closes gas to be detected, the chromatographic peak area of the perfluor isobutyronitrile and every kind of foreign gas is obtained, by described in every kind
The chromatographic peak area of foreign gas obtains described in the perfluor isobutyronitrile mixed gas to be measured every kind by the fit equation
The volume fraction of foreign gas；
The perfluor isobutyronitrile mixed gas to be measured is calculated based on the volume fraction of every kind of foreign gas in step S5
Described in perfluor isobutyronitrile purity.
2. detection method according to claim 1, which is characterized in that the chromatographic column of the gas chromatograph-mass spectrometer (GC-MS)
It comprises at least one of the following: Rtx-200 chromatographic column, GS-GasPro chromatographic column；
The chromatographic column of the gas chromatograph comprises at least one of the following: Rtx-200 chromatographic column, GS-GasPro chromatographic column,
Porapak Q chromatographic column.
3. detection method according to claim 1 or 2, which is characterized in that the step S1 includes:
Step S11 detects the perfluor isobutyronitrile mixed gas to be measured using the gas chromatography-mass spectrometry instrument, obtains
To characteristic mass-charge ratio of every kind of gas, carried out according to the characteristic mass of every kind of gas-charge ratio and NIST database
It compares, determines the ingredient of perfluor isobutyronitrile and every kind of foreign gas in the perfluor isobutyronitrile mixed gas to be measured；
Step S12 calculates every kind of foreign gas according to following formula (1) according to the chromatographic peak area of every kind of gas of gained
Discreet volume score:
Wherein, AiAnd CiThe chromatographic peak area and volume fraction of respectively i-th kind gas.
4. detection method according to claim 3, which is characterized in that the fit equation is following formula (2), described every
The volume fraction C of kind foreign gasziIt is calculated according to following formula (2):
Czi=ai×Azi+bi (2)
Wherein, AziFor the chromatographic peak area of i-th kind of foreign gas, aiAnd biFor the fitting coefficient of the standard curve.
5. detection method according to claim 4, which is characterized in that the step S5 includes:
Step S51 calculates the body of perfluor isobutyronitrile according to following formula (3) based on the volume fraction of every kind of foreign gas
Fraction CC4F7N:
CC4F7N=1- ∑ Czi (3)
Wherein, CziFor the volume fraction of i-th kind of foreign gas；
Step S52, the volume fraction of volume fraction and the perfluor isobutyronitrile based on foreign gas described in every kind, according to as follows
Formula (4) calculates the mass fraction r of every kind of foreign gaszi:
Wherein, MziFor the relative molecular mass of i-th kind of foreign gas；
Step S53 calculates the perfluor isobutyronitrile according to following formula (5) based on the mass fraction of every kind of foreign gas
Purity rC4F7N:
rC4F7N=1- ∑ rzi (5)。
6. detection method according to claim 5, which is characterized in that the volume of every kind of foreign gas in the calibrating gas
Score is identical as the order of magnitude of the discreet volume score.
7. detection method according to claim 2, which is characterized in that gas chromatography-mass spectrometry described in the step S1
The condition that instrument detects perfluor isobutyronitrile mixed gas to be measured are as follows: use split sampling mode, split ratio 50: 1, prime
Temperature is 230 DEG C, and ion source temperature is 250 DEG C, and temperature program is 35 DEG C of holdings 15min, 10 DEG C/min until 200 DEG C of holdings
5min, chromatographic column are Rtx-200 chromatographic column, flow rate of carrier gas 1.0mL/min, nebulizer gas pressure 0.5MPa；
Wherein, the Rtx-200 chromatogram column length is 105m, and internal diameter 0.32mm, film thickness is 1.50 μm.
8. detection method according to claim 2, which is characterized in that utilize the gas-chromatography described in the step S3
Instrument or the gas chromatography-mass spectrometry instrument carry out the calibrating gas to utilize the gas phase described in detection and the step S4
The condition that chromatograph or the gas chromatography-mass spectrometry instrument detect the perfluor isobutyronitrile mixed gas to be measured is equal are as follows:
Using split sampling mode, split ratio 5: 1, TCD temperature is 150 DEG C, and temperature program is 200 DEG C of holding 10min, and chromatographic column is
Porapak Q chromatographic column, flow rate of carrier gas 44mL/min, nebulizer gas pressure 0.5MPa；
Wherein, the Porapak Q chromatographic column be 80/100 mesh, a length of 6 feet, internal diameter 2mm.
9. -8 any detection method according to claim 1, which is characterized in that the foreign gas includes following at least one
Kind: air, hexafluoropropene.
10. -9 any detection method according to claim 1, which is characterized in that the background gas is helium.
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