CN107290437A - The method for measuring content of fluorine indirectly using chromatograph - Google Patents
The method for measuring content of fluorine indirectly using chromatograph Download PDFInfo
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- CN107290437A CN107290437A CN201610200550.7A CN201610200550A CN107290437A CN 107290437 A CN107290437 A CN 107290437A CN 201610200550 A CN201610200550 A CN 201610200550A CN 107290437 A CN107290437 A CN 107290437A
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- G—PHYSICS
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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Abstract
The method for measuring content of fluorine indirectly using chromatograph.The invention belongs to uranium transformation technology field, it is related to the measurement of residual fluorine gas in product gas in uranium conversion production, and in particular to remain the converted measurement method of fluorine gas in fluorination process in fluorination reaction generation furnace gas.Detected gas is pressurized by being pressurized sampling pump；Detected gas is brought into refrigerator by nitrogen as carrier gas to be cooled；Quantitative detected gas is taken to take 1ml to enter chemical reaction flow F by quantity tube after six-way valve2→Cl2, this quantitative gas sequentially passes through polytrifluorochloroethylene reactor, KCl reactors, NaF reactors, by F‑It is replaced into Cl‑And go after the removal of impurity to enter chromatograph progress Cl2The quantitative analysis of content；Cl is measured using chromatograph2Content：By calibrating template, by this Cl2Content corresponds into F2Content, the waste gas that chromatograph detection is finished, which is discharged into NaOH absorption cells, to be absorbed.The present invention is solved not used for measurement F2The problem of chromatographic column, meets the requirement of fluorination production.
Description
Technical field
The invention belongs to uranium transformation technology field, it is related to the survey of residual fluorine gas in product gas in uranium conversion production
Amount, and in particular to remain the converted measurement method of fluorine gas in fluorination process in fluorination reaction generation furnace gas.
Background technology
In the fluorination process that uranium converts production, UF6F is remained in product furnace gas2Content is one critically important
Detection content.But domestic prior art is F in measurement air2Micro content, using the work of electrochemistry
Make principle, by F2Alarm is carried out as toxic gas to use, it is impossible to use the fluorination work for converting production in uranium
Furnace gas F in sequence2The detection of content.Have in the world and F is carried out using online ultraviolet spectral analysis method2Content is examined
The instrument of survey, this instrument can meet the key technical indexes and use requirement of fluorination production.But it is online purple
External spectrum analysis meter reveals UF6To F2Measurement disturb, it is necessary to overcome.
Chromatography is a kind of method for measuring gas content, is applied in the detection of many gas contents.But it is existing
It is not directed to F also at home2The chromatographic column of measurement, it is impossible to which application chromatography is directly to F2Measure.It is comprehensive
Domestic state of the art and ability are closed, can be used F2It is converted into CL2, reuse chromatography measurement CL2
Content so that obtain F indirectly2Content.
The content of the invention
The present invention bases on our country prior art ability, solves not used for measurement F2The problem of chromatographic column, is carried
Supply one kind can be by by F2It is converted into Cl2So as to F in indirect detection furnace gas2The method of content, meets fluorine
The requirement of metaplasia production.
To reach above-mentioned purpose, the technical solution used in the present invention is：
A kind of method that utilization chromatograph measures content of fluorine indirectly, Step 1: by being pressurized sampling pump to quilt
Gas boosting is detected, detected gas is entered in chromatograph；Step 2: will be by as carrier gas by nitrogen
Detection gas is brought refrigerator into and cooled, and treats UF6After gas condensation, it will remove most of in detected gas
UF6Remaining gas outside gas delivers to downstream；Step 3: quantitative detected gas is taken, these gases warp
Cross after six-way valve takes 1ml to enter chemical reaction flow F by quantity tube2→Cl2, this quantitative gas sequentially passes through
Polytrifluorochloroethylene reactor, KCl reactors, NaF reactors, by F-It is replaced into Cl-And go after the removal of impurity
Cl is carried out into chromatograph2The quantitative analysis of content, reacts as follows：2KCl+F2=2KF+Cl2；Poly- trifluoro chlorine
Ethylene reaction device is used to make gas continuous, and KCl reactors are used for the F in quantitative gas2Be converted to Cl2It is anti-
Ying Zhu, thus contains N in the gas of post discharge2、Cl2, HF, NaF reactors be used for absorb in sample
HF；Step 4: measuring Cl using chromatograph2Content：By calibrating template, by this Cl2Content is corresponded into
F2Content, the waste gas that chromatograph detection is finished, which is discharged into NaOH absorption cells, to be absorbed.
The drainer design temperature of refrigerator is -15 DEG C, to condense UF6Gas.
Use electric-heating belt to be incubated to prevent UF on feeding process pipeline6Gas is condensed into solid blocking
Pipeline.
Having the beneficial effect that acquired by the present invention：
The present invention relates to the conversion that fluorine gas is remained in fluorination reaction generation furnace gas in fluorination process in uranium conversion production
Measuring method, using the indirect measure that fluorine gas is converted to chlorine, by chromatograph to the fluorine in furnace gas
Gas is measured.In the fluorination process that uranium converts production, mainly by UF4With F2Reaction, generates UF6
Product is gaseous state, referred to as furnace gas.To ensure UF4With F2Fully reaction, should add excessive F2.But
If excessive addition F2Not only waste material but also make postorder to residual F2Intractability increase, be unfavorable for
Environmental protection.By detecting F in furnace gas2Content, can preferably control F2Addition, can reduce cost again profit
In environmental protection.
(1) measurement Cl is chosen2Content corresponds into F2The indirect measure of content, it is to avoid key equipment F2
The chromatographic column country is without off-the-shelf, and foreign countries are to the problem of China's embargo；(2) poly- trifluoro chlorine has been selected
The mode of ethylene reaction device, KCl reactors and NaF reactors three-stage filtration, the tested gas of conversion so that
Tested gas is purified；(3) reactor filler chosen easily is bought, cheap.By to model machine
Checking examination, its elementary error≤5% (FS) meets production and application requirement, thereafter always using at the scene
On production line, stable and reliable operation.
Brief description of the drawings
Fig. 1 is F in fluorination stove furnace gas2Detection method of content schematic flow sheet；
Fig. 2 is standard specimen F in embodiment2Assay spectrogram；
Pipeline identification：A-feeding process pipeline；B-nitrogen；C-feed back process pipe；D-vacuum；
Device identification：1-supercharging sampling pump；2-refrigerator；3-six-way valve；4-polytrifluorochloroethylene is anti-
Answer device；5-KCl reactors；6-NaF reactors；7-chromatograph；8-NaOH absorption cells.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Due to F2Have stronger corrosivity, very high required to the material of detecting instrument, it is existing it is domestic also not compared with
Good detection method, is determined by the way that the F- in hex product is displaced with the Cl- close with its mole
Come, then by measuring Cl2Content extrapolates the F in former item2The method of content is come in indirect detection product
F2Content.Final detection is to use chromatography.To realize that detection is required, F2Content in-line analyzer is by two
Partial devices are constituted：1) pretreating device, by the supercharging of detection medium, removes UF6, F- displaced with Cl-
Come.2) chromatogram instrument apparatus, by the detection to Cl-, demarcates model, it is determined that corresponding F2Content.
Step 1: supercharging：
Due to technique sampling system come detection gas pressure very it is low (0~60kpa of pressure-fired, temperature~
200 DEG C), it is impossible to it is directly entered in chromatograph 7, so firstly the need of supercharging.Supercharging sampling pump 1 will can be examined
Medium is surveyed to be lifted to 0.3MPa by slight positive pressure state highest.
Step 2: condensation：
Detected gas is brought into refrigerator 2 by nitrogen b as carrier gas to be cooled, the drainer of refrigerator 2
Design temperature is -15 DEG C, to condense UF6Gas.Because UF6Gas be condensable, institute at 60 DEG C
It is incubated with employing electric-heating belt on feeding process pipeline a to prevent UF6Gas is condensed into solid and blocked up
Fill in pipeline.Treat UF6After gas is condensed substantially, major part UF will be removed in detected gas6Remaining outside gas
Gas delivers to downstream.
Step 3: taking quantitative detected gas：
These mixed gas take 1ml gas to enter chemical reaction flow after six-way valve 3 by quantity tube
(F2→Cl2).This quantitative gas sequentially passes through polytrifluorochloroethylene reactor 4, KCl reactors 5, NaF
Reactor 6, by F-It is replaced into Cl-And go after the removal of impurity to enter the progress of chromatograph 7 Cl2The quantitative analysis of content.
Key reaction is as follows：
2KCl+F2=2KF+Cl2
Wherein, the effect of polytrifluorochloroethylene reactor 4 is to eliminate column cap dead space, makes gas continuous.KCl
The effect of reactor 5 is by the F in quantitative gas2Be converted to Cl2Reaction column, thus post discharge gas
In contain N2、Cl2、HF.The main effect of NaF reactors 6 is to absorb the HF in sample, makes final inspection
The gas of survey is purer, and the error of testing result is as far as possible small.
Step 4: measuring Cl using chromatograph 72Content：
By calibrating template, by this Cl2Content corresponds into F2Content.Chromatograph 7 detects the waste gas row finished
Enter and absorbed in NaOH absorption cells 8.
Embodiment：Utilize the Oil repellent of gas chromatographic analysis hex
The Oil repellent analysis condition of gas chromatographic analysis hex
1) analysis condition
A. carrier gas：High-pure helium；
B. drainer：-15℃；
C. booster pump driving gas nitrogen：Pipeline nitrogen, 0.2MPa；
d.F2Standard Gases：15%F2, 20%F2；
e.UF6、F2Hybrid standard gas：(1)UF6=42.2%, F2=9.59%；(2)UF6=39.9%, F2=9.8%；
F.1 level converts post：100 DEG C, 2 grades of conversion posts：140 DEG C, 3 grades of conversion posts：160℃；
G. chromatograph limiting value：150 DEG C of the post case temperature limit, 100 DEG C of perfusor temperature extremes, detector temperature
200 DEG C of the limit；
H. column temperature：80 DEG C, detector temperature：130 DEG C, TCD hot-wire temperatures：160℃.
2)UF6、F2The preparation of hybrid standard gas
Sample tank is warming up to 75 DEG C, standard specimen system vacuumized, PThis=2.3kPa, is filled with UF in 2S bottles6,
PUF6=52.94kPa.It is re-filled with process pipe F2, PF2=64.45kPa.Pipeline nitrogen is filled to PAlways=120kPa.
Theoretical UF6=42.2%, F2=9.59%.Standard curve is done with this gaseous mixture.Prepare PThis=2.1kPa, PUF6=37.21
KPa, PF2=47.83kPa, PAlways=88kpa gaseous mixtures.Theoretical UF6=39.9%, F2=9.8%.Measure
F2=9.06%, see accompanying drawing 2.
Claims (3)
1. a kind of method that utilization chromatograph measures content of fluorine indirectly, it is characterised in that：Step 1: passing through
It is pressurized sampling pump (1) to be pressurized detected gas, detected gas is entered in chromatograph (7)；Step
Rapid two, bring detected gas into refrigerator (2) as carrier gas by nitrogen (b) to be cooled, treat UF6
After gas condensation, major part UF will be removed in detected gas6Remaining gas outside gas delivers to downstream；
Step 3: taking quantitative detected gas, these gases take 1ml to enter after six-way valve (3) by quantity tube
Enter to chemically react flow F2→Cl2, this quantitative gas sequentially passes through polytrifluorochloroethylene reactor (4), KCl
Reactor (5), NaF reactors (6), by F-It is replaced into Cl- and goes to enter chromatograph (7) after the removal of impurity
Carry out Cl2The quantitative analysis of content, reacts as follows：2KCl+F2=2KF+Cl2；Polytrifluorochloroethylene reactor
(4) it is used to make gas continuous, KCl reactors (5) are used for the F in quantitative gas2Be converted to Cl2It is anti-
Ying Zhu, thus contains N in the gas of post discharge2、Cl2, HF, NaF reactors (6) be used for absorb sample
In HF；Step 4: measuring Cl using chromatograph (7)2Content：By calibrating template, by this Cl2Contain
Amount corresponds into F2Content, the waste gas that chromatograph (7) detection is finished is discharged into progress in NaOH absorption cells (8)
Absorb.
2. the method that utilization chromatograph according to claim 1 measures content of fluorine indirectly, its feature exists
In：The drainer design temperature of refrigerator (2) is -15 DEG C, to condense UF6Gas.
3. the method that utilization chromatograph according to claim 1 measures content of fluorine indirectly, its feature exists
In：Electric-heating belt is used to be incubated to prevent UF on feeding process pipeline (a)6Gas is condensed into solid
Block pipeline.
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| CN201610200550.7A CN107290437A (en) | 2016-03-31 | 2016-03-31 | The method for measuring content of fluorine indirectly using chromatograph |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112946125A (en) * | 2021-02-02 | 2021-06-11 | 福建德尔科技有限公司 | Apparatus and method for analyzing hydrogen fluoride in fluorine gas |
| CN113702532A (en) * | 2021-08-30 | 2021-11-26 | 中船重工（邯郸）派瑞特种气体有限公司 | Device for measuring fluorine gas content in fluorine-containing mixed gas |
| CN114200039A (en) * | 2021-11-25 | 2022-03-18 | 天津海嘉斯迪新材料合伙企业(有限合伙) | Method for detecting HF content in fluorine gas |
| CN114577976A (en) * | 2022-03-03 | 2022-06-03 | 中昊光明化工研究设计院有限公司 | Method for measuring fluorine gas content in fluorine-nitrogen mixed gas |
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| CN1945312A (en) * | 2006-11-03 | 2007-04-11 | 石平湘 | Method for detecting micro fluorine in gas with an excimer laser |
| CN103449525A (en) * | 2013-08-30 | 2013-12-18 | 核工业理化工程研究院华核新技术开发公司 | Preparation method of molybdenum hexafluoride |
| CN104628038A (en) * | 2013-11-07 | 2015-05-20 | 中核四○四有限公司 | Fluorination technology for recovering fluorine gas |
| CN104914172A (en) * | 2014-03-10 | 2015-09-16 | 福建省邵武市永晶化工有限公司 | Method for measuring fluorine gas content in fluorine-containing mixing gas through gas chromatography method |
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Patent Citations (4)
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| CN1945312A (en) * | 2006-11-03 | 2007-04-11 | 石平湘 | Method for detecting micro fluorine in gas with an excimer laser |
| CN103449525A (en) * | 2013-08-30 | 2013-12-18 | 核工业理化工程研究院华核新技术开发公司 | Preparation method of molybdenum hexafluoride |
| CN104628038A (en) * | 2013-11-07 | 2015-05-20 | 中核四○四有限公司 | Fluorination technology for recovering fluorine gas |
| CN104914172A (en) * | 2014-03-10 | 2015-09-16 | 福建省邵武市永晶化工有限公司 | Method for measuring fluorine gas content in fluorine-containing mixing gas through gas chromatography method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112946125A (en) * | 2021-02-02 | 2021-06-11 | 福建德尔科技有限公司 | Apparatus and method for analyzing hydrogen fluoride in fluorine gas |
| CN112946125B (en) * | 2021-02-02 | 2021-11-16 | 福建德尔科技有限公司 | Apparatus and method for analyzing hydrogen fluoride in fluorine gas |
| CN113702532A (en) * | 2021-08-30 | 2021-11-26 | 中船重工（邯郸）派瑞特种气体有限公司 | Device for measuring fluorine gas content in fluorine-containing mixed gas |
| CN113702532B (en) * | 2021-08-30 | 2022-04-08 | 中船(邯郸)派瑞特种气体股份有限公司 | Device for measuring fluorine gas content in fluorine-containing mixed gas |
| CN114200039A (en) * | 2021-11-25 | 2022-03-18 | 天津海嘉斯迪新材料合伙企业(有限合伙) | Method for detecting HF content in fluorine gas |
| CN114577976A (en) * | 2022-03-03 | 2022-06-03 | 中昊光明化工研究设计院有限公司 | Method for measuring fluorine gas content in fluorine-nitrogen mixed gas |
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