CN108982190A - A kind of sulfur hexafluoride Developments of certified reference samples method - Google Patents
A kind of sulfur hexafluoride Developments of certified reference samples method Download PDFInfo
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- CN108982190A CN108982190A CN201811108012.0A CN201811108012A CN108982190A CN 108982190 A CN108982190 A CN 108982190A CN 201811108012 A CN201811108012 A CN 201811108012A CN 108982190 A CN108982190 A CN 108982190A
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- 229910018503 SF6 Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 47
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229960000909 sulfur hexafluoride Drugs 0.000 title claims abstract description 28
- 238000011161 development Methods 0.000 title claims abstract description 16
- 230000018109 developmental process Effects 0.000 title claims abstract description 16
- 238000005259 measurement Methods 0.000 claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000004575 stone Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 120
- 229910000831 Steel Inorganic materials 0.000 claims description 52
- 239000010959 steel Substances 0.000 claims description 52
- 238000005303 weighing Methods 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 12
- 238000013178 mathematical model Methods 0.000 claims description 10
- 238000004364 calculation method Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000011156 evaluation Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 238000011160 research Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000012544 monitoring process Methods 0.000 abstract description 5
- 230000002265 prevention Effects 0.000 abstract description 5
- 238000009472 formulation Methods 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000004590 computer program Methods 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000012925 reference material Substances 0.000 description 6
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- LSJNBGSOIVSBBR-UHFFFAOYSA-N thionyl fluoride Chemical compound FS(F)=O LSJNBGSOIVSBBR-UHFFFAOYSA-N 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 101000856246 Arabidopsis thaliana Cleavage stimulation factor subunit 77 Proteins 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000004164 analytical calibration Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
-
- 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
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of sulfur hexafluoride Developments of certified reference samples methods, it includes: S1: preparing calibrating gas；S2: the purity of unstripped gas in test stone gas；S3: the concentration of calibrating gas is calculated；S4: service check is carried out to calibrating gas.The present invention can lay a good foundation for the consistency and traceability of measurement result in electric power research and electrical equipment running safety monitoring, while provide reliable technical support and guarantee to accelerate the formulation and execution of the practical application and State Grid's energy security and accident prevention relevant criterion of sulfur hexafluoride gas analytical technology.
Description
Technical field
The present invention relates to sulfur hexafluoride technical field, especially a kind of sulfur hexafluoride Developments of certified reference samples method.
Background technique
Sulfur hexafluoride gas is used in large-scale emphasis electrical equipment as isolation protective material.Using SF6It is situated between as insulation
The electrical equipment of matter mainly has high-voltage circuitbreaker, transformer, mutual inductor etc..At present the equipment of 220V voltage class there are about half with
It is upper to use SF6Gas-insulated；The equipment of 330V voltage class nearly 100% uses SF6Gas-insulated；550V voltage class is set
Standby and GIS all uses SF6Gas-insulated.Equipment operation in for prevention sulfur hexafluoride electrical equipment inside existing for latency
Failure occurs, and realizes and is safely operated progress effective monitoring to electrical equipment.
To ensure that it is performed effectively, need to improve relevant detection device, analysis method and corresponding detection standard, such as
" the SF in air insulating device drafted6Gas decomposition product on-site test regulation " be related to detecting instrument calibration,
Demand of the compound mensuration to standard substance.Therefore the effect of corresponding standard substance highlights important.
Summary of the invention
In view of the above drawbacks of the prior art, it is an object of the invention to provide a kind of sulfur hexafluoride Developments of certified reference samples
Method can establish base for the consistency and traceability of measurement result in electric power research and electrical equipment running safety monitoring
Plinth, while to accelerate the practical application and State Grid's energy security mark related to accident prevention of sulfur hexafluoride gas analytical technology
Quasi- formulation and execution provides reliable technical support and guarantee.
It is realized the purpose of the present invention is technical solution in this way, a kind of sulfur hexafluoride Developments of certified reference samples method,
It includes:
S1: calibrating gas is prepared；
S2: the purity of unstripped gas in test stone gas；
S3: the concentration of calibrating gas is calculated；
S4: service check is carried out to calibrating gas.
Further, the process that calibrating gas is prepared in the step S1 is as follows:
S11: steel cylinder is carried out to vacuumize cleaning；
S12: steel cylinder quality is weighed；
S13: it is filled with unstripped gas；
S14: steel cylinder quality is weighed；
S15: it is filled with Balance Air；
S16: steel cylinder quality is weighed.
Further, detailed process is as follows for the concentration of unstripped gas in test stone gas in the step S2:
Wherein: xpureThe principal component content being expressed as in pure gas, xiThe i impurity composition content being expressed as in pure gas；
The uncertainty of measurement of principal component concentration is then as formula (2) are calculated:
Wherein: u (xpure) it is expressed as pure gas purity determination standard uncertainty；u(xi) it is expressed as impurity composition measurement standard
Uncertainty.
It further, further include the weighing having to calibrating gas after the step S2, weighing includes single-deck electronic balance
Weigh the weighing mathematical model of mathematical model and both arms electronic balance；
The weighing mathematical model of the single-deck electronic balance is as follows:
W=e (Δ mj-Δmj-1)+KΔPρair+δVρair+ΔL；
Wherein: w------- is expressed as that the quality of gas is added；
E-------- is expressed as the linear coefficient of balance reading；
Δmj--- -- is expressed as the of poor quality of sample steel cylinder and reference steel cylinder after inflation；
Δmj-1--- sample steel cylinder and reference steel cylinder is of poor quality before being expressed as inflating；
K------ is expressed as the coefficient of expansion of steel cylinder volume caused by the increase of interior of steel bottle gas pressure；
Δ P----- is expressed as the value added of interior of steel bottle gas pressure；
ρair--- --- is expressed as atmospheric density；
δ V----- is expressed as the situation of change of steel cylinder volume caused by temperature change；
Δ L---- is expressed as the quality abrasion that steel cylinder is generated in transfer process before and after the inflation；
The weighing mathematical model of the both arms electronic balance is as follows:
Wherein: ρM--- -- is expressed as the density of standard test weight；
When Mj------ is expressed as weighing sample steel cylinder after inflating, the counterbalance mass of addition；
Mj-1When ----be expressed as weighs sample steel cylinder before inflating, the counterbalance mass of addition；
The mobility of Δ b------ expression balance zero；
δVAThe situation of change of ----be expressed as balance mechanical arm volume caused by temperature change.
Further, the concentration calculation formula of the calibrating gas is as follows:
Wherein j=a, b ..., p represents the unstripped gas being added；
I=1,2 ..., n represents each component in unstripped gas；
mjThe quality being added for unstripped gas j；
xi,jFor the molar fraction of component i in unstripped gas j；
MiFor the molal weight of component i；
xkFor the molar fraction of each component k in product gas, to avoid mutually obscuring with the molar fraction of component in unstripped gas, this
Place indicates with footnote k, k=1,2 ..., n；
xk,jFor the molar fraction of component k in unstripped gas j；
The uncertainty calculation formula of concentration is (4):
The concentration and uncertainty for matching the gaseous mixture of value are calculated according to formula (3) and (4).
Further, carrying out the content of service check to calibrating gas in the step S4 includes stability, stability
Checkout procedure is as follows:
For linear fit:
For the average value of measurement result；
For the average value of time；
Slope:
Cut square:
Regression residuals:
The standard deviation of slope:
Wherein, freedom degree n-2；
If | b1| < t0.95,n-2× s (b1), for expression concentration of component to time variable without visible trend, sample stability is good
It is good；If | b1|≥t0.95,n-2×s(b1), indicate that concentration of component has notable difference to time variable, sample stability is bad；Mark
The uncertainty contribution of quasi- gas long-time stability passes through ults=s (b1) × t is provided, and wherein t is the time.
Further, carrying out the content of service check to calibrating gas in the step S4 includes calibrating gas mass value
It determines, determination process is as follows:
The uncertainty that weighing technique introduces, with ugravIt indicates；
Uniformity bleeds off pressure the uncertainty that test introduces in bottle, is expressed as uwb；
The uncertainty that long-time stability introduce, is expressed as ults；
The combined standard uncertainty u of final definite valuecIt can be obtained by formula (9):
Expanded uncertainty passes through Ur=kuc, k=2, fiducial probability=95% acquisition.
Further, further include the Evaluation of Uncertainty for having calibrating gas material mass value, evaluation procedure is as follows:
For the synthesis relative standard uncertainty u of hydrogen fluoride working calibration gas definite value in sulfur hexafluoridec-rNeed to consider with
Under several aspects uncertainty source, it may be assumed that
ugrav-r--- the relative uncertainty degree that weighing technique introduces；
uPh-r--- the relative uncertainty degree of relative humidity calibration；
ub-r--- the relative uncertainty degree of sampling pump sampling stroke；
ua-r--- the relative uncertainty degree of detection pipe observation；
The synthesis relative standard uncertainty of final definite value can be obtained by formula (10):
It passes through U with respect to expanded uncertaintyr=kuc-r, k=2, fiducial probability=95% acquisition.
By adopting the above-described technical solution, the present invention has the advantage that: the present invention can be electric power research and electricity
The consistency of measurement result and traceability are laid a good foundation in the monitoring of gas equipment safety operation, while to accelerate sulfur hexafluoride gas
The formulation and execution of the practical application and State Grid's energy security and accident prevention relevant criterion of analytical technology provide reliable
Technical support and guarantee.
Other advantages, target and feature of the invention will be illustrated in the following description to a certain extent, and
And to a certain extent, based on will be apparent to those skilled in the art to investigating hereafter, Huo Zheke
To be instructed from the practice of the present invention.
Detailed description of the invention
Detailed description of the invention of the invention is as follows:
Fig. 1 is the flow diagram of sulfur hexafluoride Developments of certified reference samples method.
Fig. 2 is the flow diagram for preparing calibrating gas.
Fig. 3 is calibrating gas long-time stability research experiment flow diagram.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
Embodiment, as shown in Figure 1 to Figure 3；A kind of sulfur hexafluoride Developments of certified reference samples method, it includes:
S1: calibrating gas is prepared；
S2: the purity of unstripped gas in test stone gas；
S3: the concentration of calibrating gas is calculated；
S4: service check is carried out to calibrating gas.
The process that calibrating gas is prepared in the step S1 is as follows:
S11: steel cylinder is carried out to vacuumize cleaning；
S12: steel cylinder quality is weighed；
S13: it is filled with unstripped gas；
S14: steel cylinder quality is weighed；
S15: it is filled with Balance Air；
S16: steel cylinder quality is weighed.
Detailed process is as follows for the concentration of unstripped gas in test stone gas in the step S2:
Wherein: xpureThe principal component content being expressed as in pure gas, xiThe i impurity composition content being expressed as in pure gas；
The uncertainty of measurement of principal component concentration is then as formula (2) are calculated:
Wherein: u (xpure) it is expressed as pure gas purity determination standard uncertainty；u(xi) it is expressed as impurity composition measurement standard
Uncertainty.
The purity and uncertainty for the pure gas that the present invention uses see the table below 1~table 5.
1 sulfur hexafluoride purity of table and uncertainty
2 carbon dioxide purity of table and uncertainty
3 carbon tetrafluoride purity of table and uncertainty
Table 4 is fluorinated thionyl purity and uncertainty
Table 5 is fluorinated sulfonyl purity and uncertainty
When (uniform) distribution of rectangle is presented in the concentration of some component in the concentration range of 0~b, mathematical expectation
(concentration) is a=b/2, and corresponding standard uncertainty is
For SOF2、SO2F2Long light path FTIR transform infrared spectroscopy instrument is respectively adopted in the analysis of two kinds of material purities
(Nicolet-5700) and gas chromatographymass spectrometry instrument (GC-MS-5970) carries out purity analysis, is carried out using area normalization method
Purity definite value.
It further include the weighing having to calibrating gas after the step S2, weighing includes the weighing mathematics of single-deck electronic balance
The weighing mathematical model of model and both arms electronic balance；Single-deck electronic balance (sensibility reciprocal 1mg), both arms balance (sensibility reciprocal 1mg)；
The weighing mathematical model of the single-deck electronic balance is as follows:
W=e (Δ mj-Δmj-1)+KΔPρair+δVρair+ΔL；
Wherein: w------- is expressed as that the quality of gas is added；
E-------- is expressed as the linear coefficient of balance reading；
Δmj--- -- is expressed as the of poor quality of sample steel cylinder and reference steel cylinder after inflation；
Δmj-1--- sample steel cylinder and reference steel cylinder is of poor quality before being expressed as inflating；
K------ is expressed as the coefficient of expansion of steel cylinder volume caused by the increase of interior of steel bottle gas pressure；
Δ P----- is expressed as the value added of interior of steel bottle gas pressure；
ρair--- --- is expressed as atmospheric density；
δ V----- is expressed as the situation of change of steel cylinder volume caused by temperature change；
Δ L---- is expressed as the quality abrasion that steel cylinder is generated in transfer process before and after the inflation；
According to the model, it is as shown in table 6 to calculate standard uncertainty corresponding to the gas that different quality is added in steel cylinder.
The uncertainty of gaseous mass is added in 6 single-deck electronic balance weighing steel cylinder of table
The weighing mathematical model of the both arms electronic balance is as follows:
Wherein: ρM--- -- is expressed as the density of standard test weight；
When Mj------ is expressed as weighing sample steel cylinder after inflating, the counterbalance mass of addition；
Mj-1When ----be expressed as weighs sample steel cylinder before inflating, the counterbalance mass of addition；
The mobility of Δ b------ expression balance zero；
δVAThe situation of change of ----be expressed as balance mechanical arm volume caused by temperature change.
According to the model, standard uncertainty such as the following table 7 institute corresponding to the gas that different quality is added in steel cylinder is calculated
Show.
The uncertainty of gaseous mass is added in 7 both arms electronic balance weighing steel cylinder of table
It can be seen that either single-deck electronic balance or both arms balance by table 6 and table 7, weigh behaviour meeting balance
Under conditions of the Quality Control of work requires, the gas within 1.5g~10g is weighed, standard uncertainty is both less than 8mg, weighs 10g
Gas within~70g, standard uncertainty are both less than 12mg.To simplify the calculation, gas is added in calculating steel cylinder in this project
When the uncertainty of weight, if gaseous mass, within 1.5g~10g, uncertainty is unified for 8mg；If gas
Quality is within 10g~70g, then its uncertainty is unified for 12mg.When weighing the gas for being less than 1.5g, the balance sense that uses
Amount is 0.1mg, and the uncertainty weighed is not more than 1mg.To simplify the calculation, when the gas for being less than 1.5g using micro tube weighing
When, uncertainty is unified for 1mg.
The concentration calculation formula of the calibrating gas is as follows:
Wherein j=a, b ..., p represents the unstripped gas being added；
I=1,2 ..., n represents each component in unstripped gas；
mjThe quality being added for unstripped gas j；
xi,jFor the molar fraction of component i in unstripped gas j；
MiFor the molal weight of component i；
xkFor the molar fraction of each component k in product gas, to avoid mutually obscuring with the molar fraction of component in unstripped gas, this
Place indicates with footnote k, k=1,2 ..., n；
xk,jFor the molar fraction of component k in unstripped gas j；
The uncertainty calculation formula of concentration is (4):
The concentration and uncertainty for matching the gaseous mixture of value are calculated according to formula (3) and (4).Calculated result is shown in Table 8.
The concentration and uncertainty of 8 gaseous mixture of table
It can see from table 8, CO2/SF6、CF4/SF6、SOF2/F6And SO2F2/SF6The stardard uncertairty that gravimetric method is prepared
Degree is respectively less than 0.2%；HF/SF6Relative standard uncertainty is less than 0.6%.
Carrying out the content of service check to calibrating gas in the step S4 includes stability, the checkout procedure of stability
It is as follows:
For linear fit:
For the average value of measurement result；
For the average value of time；
Slope:
Cut square:
Regression residuals:
The standard deviation of slope:
Wherein, freedom degree n-2；
If | b1| < t0.95,n-2×s(b1), for expression concentration of component to time variable without visible trend, sample stability is good
It is good；If | b1|≥t0.95,n-2×s(b1), indicate that concentration of component has notable difference to time variable, sample stability is bad；Mark
The uncertainty contribution of quasi- gas long-time stability passes through ults=s (b1) × t is provided, and wherein t is the time.
As shown in figure 3, in order to examine or check gas reference material its component magnitude that invention is developed under the condition of storage of room temperature
Long-time stability, the tracking changed over time to prepared mixed gas examines or check, and the results are shown in Table 9 to table 12.
The Journal of Sex Research steady in a long-term of carbon dioxide calibrating gas (~50 μm of ol/mol) in 9. sulfur hexafluoride of table
The Journal of Sex Research steady in a long-term of carbon tetrafluoride calibration gas (~50 μm of ol/mol) in 10. sulfur hexafluoride of table
The Journal of Sex Research steady in a long-term of thionyl calibrating gas (~50 μm of ol/mol) is fluorinated in 11. sulfur hexafluoride of table
The Journal of Sex Research steady in a long-term of sulfonyl calibrating gas (~50 μm of ol/mol) is fluorinated in 12. sulfur hexafluoride of table
The content for carrying out service check to calibrating gas in the step S4 includes the determination of calibrating gas mass value, really
It is as follows to determine process:
The uncertainty that weighing technique introduces, with ugravIt indicates；
Uniformity bleeds off pressure the uncertainty that test introduces in bottle, is expressed as uwb；
The uncertainty that long-time stability introduce, is expressed as ults；
The combined standard uncertainty u of final definite valuecIt can be obtained by formula (9):
Expanded uncertainty passes through Ur=kuc, k=2, fiducial probability=95% acquisition.
The Composite Seismogram of gas reference material is shown in Table 13:
13 uncertainty combination table of table
As can be seen from Table 13: for four kinds of gas reference materials in table, it is opposite in research range for constituent content
Expanded uncertainty is no more than 3.0%.
Further include the Evaluation of Uncertainty for having calibrating gas material mass value, evaluation procedure is as follows:
For the synthesis relative standard uncertainty u of hydrogen fluoride working calibration gas definite value in sulfur hexafluoridec-rNeed to consider with
Under several aspects uncertainty source, it may be assumed that
ugrav-r--- the relative uncertainty degree that weighing technique introduces；
uPh-r--- the relative uncertainty degree of relative humidity calibration；
ub-r--- the relative uncertainty degree of sampling pump sampling stroke；
ua-r--- the relative uncertainty degree of detection pipe observation；
The synthesis relative standard uncertainty of final definite value can be obtained by formula (10):
It passes through U with respect to expanded uncertaintyr=kuc-r, k=2, fiducial probability=95% acquisition.It is shown in Table 14:
Table 14HF/SF6Working calibration gas uncertainty combination table
By the way that the comprehensive of series standard substance in this subject study is examined or check and evaluated, project research achievement reaches technology and refers to
Pre-provisioning request is marked, gas reference material definite value uncertainty is shown in Table 15:
The uncertainty of 15 gas reference material definite value of table
| Standard substance title | Content (μm ol/mol) | Ur(k=2), % |
| CO2/SF6 | 20~~100 | 3 |
| CF4/SF6 | 20~~100 | 3 |
| SOF2/SF6 | 50~100 | 3 |
| SO2F2/SF6 | 50~100 | 3 |
| *HF/SF6 | ~100 | 20 |
*HF/SF6Working calibration gas.
Other indexs:
A. packaged form: 4 liters of steel cylinders (use carbon steel bottle or aluminium alloy steel cylinder for CO2/SF6 and CF4/SF6 component；It is right
Fluorine cylinder is applied using inner wall in SOF2/SF6 and SO2F2/SF6 component).
B. pressure limit: 2MPa → 0.5MPa is used；
C. effective life: 6 months (for CO2/SF6, CF4/SF6, SOF2/SF6 and SO2F2/SF6)；
3 months (for HF/SF6)
The gas reference material that the present invention develops is measurement result in electric power research and electrical equipment running safety monitoring
Consistency and traceability are laid a good foundation, while to accelerate the practical application and State Grid's energy of sulfur hexafluoride gas analytical technology
The formulation and execution of source safety and accident prevention relevant criterion provide reliable technical support and guarantee.
It should be understood by those skilled in the art that, embodiments herein can provide as method, system or computer program
Product.Therefore, complete hardware embodiment, complete software embodiment or reality combining software and hardware aspects can be used in the application
Apply the form of example.Moreover, it wherein includes the computer of computer usable program code that the application, which can be used in one or more,
The computer program implemented in usable storage medium (including but not limited to magnetic disk storage, CD-ROM, optical memory etc.) produces
The form of product.
The application is referring to method, the process of equipment (system) and computer program product according to the embodiment of the present application
Figure and/or block diagram describe.It should be understood that every one stream in flowchart and/or the block diagram can be realized by computer program instructions
The combination of process and/or box in journey and/or box and flowchart and/or the block diagram.It can provide these computer programs
Instruct the processor of general purpose computer, special purpose computer, Embedded Processor or other programmable data processing devices to produce
A raw machine, so that being generated by the instruction that computer or the processor of other programmable data processing devices execute for real
The device for the function of being specified in present one or more flows of the flowchart and/or one or more blocks of the block diagram.
These computer program instructions, which may also be stored in, is able to guide computer or other programmable data processing devices with spy
Determine in the computer-readable memory that mode works, so that it includes referring to that instruction stored in the computer readable memory, which generates,
Enable the manufacture of device, the command device realize in one box of one or more flows of the flowchart and/or block diagram or
The function of being specified in multiple boxes.
These computer program instructions also can be loaded onto a computer or other programmable data processing device, so that counting
Series of operation steps are executed on calculation machine or other programmable devices to generate computer implemented processing, thus in computer or
The instruction executed on other programmable devices is provided for realizing in one or more flows of the flowchart and/or block diagram one
The step of function of being specified in a box or multiple boxes.
Finally it should be noted that: the above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, to the greatest extent
Invention is explained in detail referring to above-described embodiment for pipe, it should be understood by those ordinary skilled in the art that: still
It can be with modifications or equivalent substitutions are made to specific embodiments of the invention, and without departing from any of spirit and scope of the invention
Modification or equivalent replacement, should all cover within the scope of the claims of the present invention.
Claims (8)
1. a kind of sulfur hexafluoride Developments of certified reference samples method, which is characterized in that the method comprises the following steps:
S1: calibrating gas is prepared；
S2: the purity of unstripped gas in test stone gas；
S3: the concentration of calibrating gas is calculated；
S4: service check is carried out to calibrating gas.
2. sulfur hexafluoride Developments of certified reference samples method as described in claim 1, which is characterized in that prepare mark in the step S1
The process of quasi- gas is as follows:
S11: steel cylinder is carried out to vacuumize cleaning；
S12: steel cylinder quality is weighed；
S13: it is filled with unstripped gas；
S14: steel cylinder quality is weighed；
S15: it is filled with Balance Air；
S16: steel cylinder quality is weighed.
3. sulfur hexafluoride Developments of certified reference samples method as described in claim 1, which is characterized in that examine mark in the step S2
Detailed process is as follows for the concentration of unstripped gas in quasi- gas:
Wherein: xpureThe principal component content being expressed as in pure gas, xiThe i impurity composition content being expressed as in pure gas；
The uncertainty of measurement of principal component concentration is then as formula (2) are calculated:
Wherein: u (xpure) it is expressed as pure gas purity determination standard uncertainty；u(xi) to be expressed as impurity composition measurement standard not true
Fixed degree.
4. sulfur hexafluoride Developments of certified reference samples method as described in claim 1, which is characterized in that further include after the step S2
There is the weighing to calibrating gas, weighing includes the weighing mathematical model of single-deck electronic balance and the weighing number of both arms electronic balance
Learn model；
The weighing mathematical model of the single-deck electronic balance is as follows:
W=e (Δ mj-Δmj-1)+KΔPρair+δVρair+ΔL；
Wherein: w------- is expressed as that the quality of gas is added；
E-------- is expressed as the linear coefficient of balance reading；
Δmj--- -- is expressed as the of poor quality of sample steel cylinder and reference steel cylinder after inflation；
Δmj-1--- sample steel cylinder and reference steel cylinder is of poor quality before being expressed as inflating；
K------ is expressed as the coefficient of expansion of steel cylinder volume caused by the increase of interior of steel bottle gas pressure；
Δ P----- is expressed as the value added of interior of steel bottle gas pressure；
ρair--- --- is expressed as atmospheric density；
δ V----- is expressed as the situation of change of steel cylinder volume caused by temperature change；
Δ L---- is expressed as the quality abrasion that steel cylinder is generated in transfer process before and after the inflation；
The weighing mathematical model of the both arms electronic balance is as follows:
Wherein: ρM--- -- is expressed as the density of standard test weight；
When Mj------ is expressed as weighing sample steel cylinder after inflating, the counterbalance mass of addition；
Mj-1When ----be expressed as weighs sample steel cylinder before inflating, the counterbalance mass of addition；
The mobility of Δ b------ expression balance zero；
δVAThe situation of change of ----be expressed as balance mechanical arm volume caused by temperature change.
5. sulfur hexafluoride Developments of certified reference samples method as described in claim 1, which is characterized in that the concentration of the calibrating gas
Calculation formula is as follows:
Wherein j=a, b ..., p represents the unstripped gas being added；
I=1,2 ..., n represents each component in unstripped gas；
mjThe quality being added for unstripped gas j；
xi,jFor the molar fraction of component i in unstripped gas j；
MiFor the molal weight of component i；
xkIt is used herein for the molar fraction of each component k in product gas to avoid mutually obscuring with the molar fraction of component in unstripped gas
Footnote k expression, k=1,2 ..., n；
xk,jFor the molar fraction of component k in unstripped gas j；
The uncertainty calculation formula of concentration is (4):
The concentration and uncertainty for matching the gaseous mixture of value are calculated according to formula (3) and (4).
6. sulfur hexafluoride Developments of certified reference samples method as described in claim 1, which is characterized in that standard in the step S4
The content that gas carries out service check includes stability, and the checkout procedure of stability is as follows:
For linear fit:
For the average value of measurement result；
For the average value of time；
Slope:
Cut square:
Regression residuals:
The standard deviation of slope:
Wherein, freedom degree n-2；
If | b1| < t0.95,n-2×s(b1), for expression concentration of component to time variable without visible trend, sample stability is good；Such as
Fruit | b1|≥t0.95,n-2×s(b1), indicate that concentration of component has notable difference to time variable, sample stability is bad；Standard Gases
The uncertainty contribution of body long-time stability passes through ults=s (b1) × t is provided, and wherein t is the time.
7. sulfur hexafluoride Developments of certified reference samples method as described in claim 1, which is characterized in that standard in the step S4
The content of gas progress service check includes the determination of calibrating gas mass value, and determination process is as follows:
The uncertainty that weighing technique introduces, with ugravIt indicates；
Uniformity bleeds off pressure the uncertainty that test introduces in bottle, is expressed as uwb；
The uncertainty that long-time stability introduce, is expressed as ults；
The combined standard uncertainty u of final definite valuecIt can be obtained by formula (9):
Expanded uncertainty passes through Ur=kuc, k=2, fiducial probability=95% acquisition.
8. sulfur hexafluoride Developments of certified reference samples method as claimed in claim 7, which is characterized in that further include having calibrating gas object
The Evaluation of Uncertainty of matter mass value, evaluation procedure are as follows:
For the synthesis relative standard uncertainty u of hydrogen fluoride working calibration gas definite value in sulfur hexafluoridec-rIt need to consider following several
The uncertainty source of a aspect, it may be assumed that
ugrav-r--- the relative uncertainty degree that weighing technique introduces；
uPh-r--- the relative uncertainty degree of relative humidity calibration；
ub-r--- the relative uncertainty degree of sampling pump sampling stroke；
ua-r--- the relative uncertainty degree of detection pipe observation；
The synthesis relative standard uncertainty of final definite value can be obtained by formula (10):
It passes through U with respect to expanded uncertaintyr=kuc-r, k=2, fiducial probability=95% acquisition.
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Application publication date: 20181211 |